Photovoltaic Materials (Richard H. Bube)

Photovoltaic Materials
SERIES ON PROPERTIES OF SEMICONDUCTOR MATERIALS
Series Editor: Ron C. Newman
Forthcoming
Semiconductor Defect Modelling ab initio Methods

R. Jones and P. R. Briddon
Muon Spectroscopy of Semiconductors

S. F. J. Cox and R. Lichti
Complex Semiconductor Defects

M. Spaeth and F. Koschnick
. . Properties of Semiconductor Materials - Vol. 1
Photovoltuic
M uteriuIs
Richard H, Bube
Stanford University, USA
Imperial College Press

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Bube, Richard H., 1927-
Photovoltaic materials / Richard H. Bube.
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ISBN 1-86094-065-X
1. Photovoltaic cells -- Materials. 2. Semiconductors. I. Title.
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The heavens are telling the glory of God;
and the firmament proclaims His handiwork. . . .
In [the heavens] He has set a tent for the sun ...
Its rising is from the end of the heavens . . .
and there is nothing hid from its heat.
Psalm 19:1,4,6
This book is dedicated to Betty Jane Meeker Bube,

my beloved wife of 48 years,
who went home to be with the Lord
when this book was in preparation.
PREFACE
Interest in photovoltaics has grown rapidly during the last half of the current
century. The importance of alternative energy sources has increased in signif-
icance both for energy supply and ecological conservation reasons. In spite of
limitations due to short-term economic considerations, research and develop-
ment of photovoltaic solar cells has increased and is playing an increasingly
practical role all over the world.
The performance of photovoltaic solar cells is intimately related to the
properties of the materials from which they are made, and many materials
science problems are encountered in the understanding of existing solar cells
and the development of more efficient, less costly and more stable cells.
Every semiconducting material in a suitable electronic environment is ca-
pable of exhibiting properties that might properly be called “photovoltaic” , i.e.
the generation of an electric current and potential difference under absorbed
illumination. What may be considered surprising, therefore, is that so few
materials are known that are able to form photovoltaic devices with sufficient
efficiency to make them of potential interest for practical applications. Allow-
ing for the additional existence of a number of solid solution compounds based
on this small number, it is still noteworthy that only the following materials
have exhibited a solar efficiency in excess of ten percent: silicon, gallium ar-
senide, indium phosphide, cadmium telluride, copper indium diselenide, and
cuprous sulfide. Of these the most versatile is silicon, which can be used to
produce efficient cells in single crystal, polycrystalline or amorphous form.
It is the purpose of this book to describe the properties of these materials
that play an important role in their photovoltaic applications, and to discuss
the experimental and theoretical developments that have led to the leading
contenders among photovoltaic cells for practical applications today. In con-
junction with this is included (where appropriate) a briefer discussion of other
systems that have been tested but have been found to exhibit major prob-
lems primarily in the areas of low efficiency or poor stability under operating
conditions, as well as systems that are considered exploratory today but may
develop into devices of interest in the future. It is not the purpose of the book
to attempt an exhaustive history of the rapidly expanding field of photovoltaic
materials, but to concentrate instead, primarily on developments in the last
decade.
vii
viii Preface
The book starts with a summary of the major properties of the semiconduc-
tor junctions that are involved in conventional photovoltaic devices, together
with the typical quantitative relationships that describe electrical transport in
these junctions. The major purpose of this summary is t o provide a common
framework for the discussions to follow, and it is assumed that the reader has
a basic grounding in semiconductor electronics. It is anticipated that the book
will be used in a teaching or research environment.
The focus of the book is on the materials properties important for photo-
voltaic applications, and does not deal in detail with device design or systems
considerations, except where these are essential to the discussion. It is based
on over twenty-five years of research experience, which has touched a t one
time or another on properties relevant to photovoltaic applications of all of the
major materials.
The book covers research done by a wide variety of investigators in many
countries. I am grateful for the assistance that has been given to me by many
colleagues from all over the world in acquiring reprints of key research papers.
In my own program a t Stanford University, thirty-one students have com-
pleted their Ph.D. research on photovoltaic materials and have added many
significant memories in the process. I gratefully acknowledge support for that
research from the .Air Force Materials Laboratory a t Wright-Patterson Air
Force Base, the NASA Lewis Research Center, the National Science Founda-
tion - Research Aimed at National Needs (NSF-RANN), ERDA, the Division
of Basic Energy Science (BES) of the Department of Energy, the Solar En-
ergy Research Institute (SERI), the Electric Power Research Institute (EPRI),
ARC0 Solar, and the National Renewable Energy Laboratory (NREL). The
research benefited throughout from facilities made available t o Stanford Uni-
versity by the National Science Foundation through the Center for Materials
Research at Stanford University.
I am indebted to the many Visiting Scholars from all over the world who
have participated in this research, and particularly to my immediate colleagues
at Stanford: Dr. Alan L. Fahrenbruch, Dr. David Redfield, and Dr. Adolfo
Lopez-Otero. I am also most thankful for the sun that has shone in my own
life throughout these years because of the constant love and support of my wife
Betty.
Stanford 1997 Richard H. Bube

CONTENTS
Preface vii
Chapter 1. Photovoltaic Materials and Phenomena 1
1.1. Overview 1
1.2. Applications of Photovoltaics 12
1.3. Types of Semiconductor Junctions 16
1.4. More Detailed Photovoltaic Models 25
1.5. Photovoltaic Materials 32
Chapter 2. Crystalline Silicon 34
2.1. Overview 34
2.2. Doping and Lifetime 36
2.3. Major Sources of Recombination 37
2.4. Development of Single Crystal Silicon Solar Cells 41
2.5. Increasing the Efficiency of Silicon Cells 53
2.6. Novel Structures 56
2.7. Thin Multicrystalline Silicon Solar Cells 57
2.8. Microcrystalline Silicon 66
Chapter 3. Amorphous Silicon 68
3.1. Overview 68
3.2. Electronic Structure and Dangling Bond
Defects in a-Si: H 71
3.3. Modes of Defect Generation 74
3.4. Models for Dangling Bond Defects 79
3.5. Overview of a-Si: H Solar Cells 91
3.6. Variations in Deposition Techniques 96
3.7. Material Transport Properties Important
for Solar Cells 97
3.8. Solar Cell Stability 100
3.9. Amorphous Silicon Alloys 106
3.10. Hybrid Solar Cells Involving a-Si : H 109
Chapter 4. Gallium Arsenide and Other 111-V Materials 111
4.1. Overview 111
4.2. GaAs Fabrication Techniques 115
4.3. GaAs-based Solar Cell Development 116
4.4. InP-based Solar Cells 126
4.5. Hybrid Multijunction Cells 131
4.6. Radiation Resistance 132
Chapter 5. Cadmium Telluride and Other 11-VI Materials 135
5.1. Overview 135
ix
x Contents
5.2. Surface and Contact Properties 141

5.3. Doping of p t y p e CdTe 149
5.4. Post-deposition Processing and Interface
Properties 154
5.5. SIS Junctions 159
5.6. Grain Boundary Effects 160
5.7. Film Deposition by Vacuum Evaporation 164
5.8. Film Deposition by Close-Spaced Vapor
Transport (CSVT) [or Close-Spaced
Sublimation (CSS)] 167
5.9. Film Deposition by Spray Pyrolysis 171
5.10. Other Film Deposition Methods 175
5.11. CdTe Alloys 181
5.12. Other 11-VI Junctions 183
Chapter 6. Copper Indium Diselenide and Other
I-111-VI Materials 184
6.1. Overview 184
6.2. Materials Properties of CuInSez 190
6.3. Fabrication Techniques 196
6.4. Solar Cell Developments 201
6.5. Related Alloys and Materials 206
6.6. Multijunction Cells 213
6.7. General Materials Considerations 213
Chapter 7. Other Materials of Interest for Solar Cells 215
7.1. Overview 215
7.2. Cuprous Oxide 215
7.3. Zinc Phosphide 216
7.4. Tungsten Diselenide 218
7.5. Polymers and Organic Materials 219
7.6. Semiconductor/Liquid Junctions 222
7.7. New Materials and Structures 223
References 225
Bibliography 268
Review Publications 270
Index 277
CHAPTER 1
PHOTOVOLTAIC CELLS
AND PHENOMENA
1.1. Overview
A material (or device) is said to be “photovoltaic” when exposure of the ma-
terial to light that can be absorbed by the material is able to transform the
energy of the light photons into electrical energy in the form of a current and
voltage. The concept is simple and the number of materials that are able to
exhibit photovoltaic characteristics is large. What is not large, however, is the
number of such materials or devices that are able t o make the transformation
of solar radiation to electrical energy with high efficiency, of the order of 20%,
at low cost, and with high stability under operation.
The development of photovoltaic cells can be dated originally to Becquerel’s
discovery in 1839 of a photovoltage produced by the action of light on a n
electrode in an electrolyte solution (Becquerel, 1839). About 40 years later,
Adams and Day observed the photovoltaic effect in selenium (Adams and Day,
1877). Solar efficiencies of about 1% characterized selenium and copper oxide
cells by about 1914. The modern era of semiconductor photovoltaics started
in 1954 when Chapin, Fuller and Pearson obtained a solar efficiency of 6% for
a silicon junction cell (Chapin et al., 1954), a value that was increased t o 14%
by 1958, and to 28% by 1988 (Verlinden et al., 1988). The year 1954 also
dates the announcement of the first all-thin-film cell composed of a Cu,S/CdS
junction (Reynolds et al., 1954) with an efficiency of 6%, later increased to over
9% (Bragagnolo et al., 1980) , which unfortunately had the stability problems
described below. The first mention of a cell based on GaAs was for a 4%
p-n homojunction in 1956 (Jenny et al., 1956); later developments were to
produce cells with efficiencies greater than 30%, as discussed in Chapter 4.
Concern about energy resources motivated a strong surge of interest in solar
cells for terrestrial applications in the early 1970’s. In spite of the fact that the
1980’s and ’90s have been a period in which public and government support for
photovoltaics have been underemphasized, considerable activity and progress
in research and development of solar cells has continued.
1
2 Photovoltaic Materials
The Photovoltaic Process

The basic concept of the photovoltaic process is also simple. When light with
photon energy greater than the band gap is absorbed by a semiconductor
material, free electrons and free holes are formed by optical excitation in the
semiconductor. The crucial characteristic needed for the photovoltaic effect is
the presence of some kind of internal electric field (from any of a variety of
causes: e.g. different doping in different regions, contacts, surfaces, etc.) that
is able to separate the freed electrons and holes so that they can pass out of
the material into the external circuit before they recombine with one another.
The flow of carriers into the external circuit constitutes a reverse electrical
current density, J amp cm-2, which, under short-circuit conditions, is known
as the short-circuit current density, Js,. (For consistency, in this book the term
current will always mean current density J unless specifically stated otherwise.
The total current I = J A , where A is the area through which the current
flows.) At the same time, the separation of the charges sets up a forward
ZnSe
.-. ABSORPTION EDGE
I n 1
WAVELENGTH, p m
Fig. 1.1. Average solar spectrum a t the surface of the earth, with the band gaps of various
semiconductors indicated. As discussed in this chapter, a homojunction or a front-wall
heterojunction will absorb all the solar spectrum t o the left of the indicated absorption edge
for a particular material. A back-wall heterojunction will absorb the solar spectrum between
the two band gaps of the materials making up the heterojunction. (Reprinted from R. H.
Bube, "Solar Cells" in Handbook on Semiconductors. Device Physics. Vol. 4C. C. Hilsum,
ed., 1993, p. 797, with kind permission from Elsevier Science - NL, Sara Burgerhartstraat
25, 1055 KV Amsterdam, T h e Netherlands.)
Photovoltaic Cells and Phenomena 3
potential difference between the two ends of the material, 4, which under open-
circuit conditions is known as the open-circuit voltage, &. The polarity of
the open-circuit voltage, therefore, is such as to drive electrons (holes) in the
opposite direction (the forward-bias direction) to that of the electron (hole)
motion in the short-circuit current. Specific examples of photovoltaic systems
are described in more detail in following sections of this chapter.
Maximizing Photovoltaic Performance

It is desirable to maximize both J,, and +oc. In order to maximize J,,, it is
desirable (1) to absorb as much of the incident light as possible, i.e. t o have
a small band gap with high absorption over a wide energy range, and (2) to
Fig. 1.2. An early calculation of the theoretical solar efficiency versus semiconductor band
gap for ideal p-n homojunction cells with no surface recombination loss. Curves are shown
for two different junction transport mechanisms: (top) A = 1 for injection dominated current
and (bottom) A = 2 for recombination in the depletion layer. (Reprinted with permission
from J. J. Loferski, J . Appl. Phys. 27, 777 (1956). Copyright 1956, American Institute of
Physics.)
have material properties such that the photoexcited electrons and holes are able
to be collected by the internal electric field and pass into the external circuit
before they recombine, i.e. a material with a high minority carrier lifetime
and mobility. In order to maximize &, it is also preferred to have the forward
current driven by the photo-induced potential difference be as small as possible
since this current will reduce the potential difference set up by light. The
details of this forward current depend critically on the actual mechanisms of
transport involved, but in general the forward current varies inversely as the
band gap of the material.
From these two purely qualitative considerations, therefore, it may be
concluded that there will be a n optimum band gap or band gap range for
PHOTON ENERGY ( e V )
Fig. 1.3. Optical absorption coefficients of various single-crystal semiconductors commonly
used in photovoltaic devices. (Reprinted with permission from A. L. Fahrenbruch and
R. H. Bube, Fundamentals of Solar Cells: Photovoltaic Solar Energy Conversion, Copy-
right 1983, Academic Press, Orlando, FL.)
maximizing both J,, and q50c, and hence the efficiency of the photovoltaic de-
vice itself. For interaction with the solar spectrum (see Fig. l.l),this optimum
band gap range lies approximately between 1.2 and 1.8 eV. The results of one
of the first calculations of the dependence of efficiency on band gap for two
different types of junction current are pictured in Fig. 1.2 (Loferski, 1956). De-
tails of the concepts described in the figure caption are discussed later in this
chapter. For comparison, Fig. 1.3 shows the dependence of optical absorption
coefficients on photon energy for various single-crystal semiconductors used in
photovoltaic devices (Fahrenbruch and Bube, 1983).
Description of Solar Spectrum

As shown in Fig. 1.1, the sun is a complex radiator with a spectrum that can
be approximated by the spectrum of a 6050 K black body. This spectrum is
then modified by temperature variations across the sun’s disk, the effects of
the solar atmosphere, Fraunhofer absorption lines, and the path length of the
radiation through the earth’s atmosphere, where the primary effects are due
to water content, turbidity, ozone, cloudiness, and ground reflection.
For terrestrial applications, the path length through the atmosphere is of
fundamental importance. This path length can be conveniently described in
terms of an equivalent “air mass”, m,. If a zenith angle z is defined as the angle
from the normal to the plane containing the horizon circle, which describes the
declination of the sun, the path length for a zenith angle z is just sec z times the
path length for z = 0, and the air mass m,, is defined as m, = secz. Specific
solar spectra are labeled AMm, (read: air mass m,). AM0 corresponds to
the solar spectrum in outer space; AM1 to the solar spectrum a t the earth’s
surface for the sun overhead. AM2 corresponds to an approximately average
solar spectrum at the earth’s surface.
Simplest Photovoltaic Device

In order to make these introductory concepts more specific, let us consider the
simplest photovoltaic device and the mathematical description of the electrical
properties of such a device. In subsequent sections of this chapter, we summa-
rize some of the possible variations and complications in more detail. Here we
use the simple equivalent circuit for a photovoltaic cell as shown in Fig. 1.4,
including a current generator corresponding to photoexcitation, a diode con-
taining the internal electric field necessary for driving photoexcited carriers t o
the external circuit, a series resistance, R,, and a parallel resistance, Rp. We
Fig. 1.4. Simple equivalent circuit for a photovoltaic cell, including a current generator with
total light current I L , a diode with total dark current I D , a series resistance R,, and a parallel
resistance R,. (Reprinted with permission from R. H. Bube, Photoelectronic Properties of
Semiconductors, Copyright 1992, Cambridge University Press.)
make the model even simpler by considering at this point a n “ideal device”
with R, = 0 and R, = co. If we make the simple assumption that the current
generated by light can simply be added to the current flowing in the dark ( “SU-
perposition”), then the current density J flowing in the device in the presence
of photoexcitation can be expressed as
J = J,,[exp(q+/AkT) - 11 - J L (1.1)
Here the first term on the right of Eq. (1.1) is the forward current driven
by the voltage 4, and the second term is the reverse current associated with
photoexcitation. J,, is often called the “reverse saturation current” of the diode,
+
the value of J in the dark for large negative values of in ideal junctions, which
depends on the actual transport mechanism for the diode current (J,, is often
called simply the “pre-exponential coefficient” in practical devices for which
reverse saturation may not occur), and A is the so-called “ideality factor”
that has a value depending on the mechanism of the junction transport (e.g.,
A = 1 if the transport process is diffusion, A z 2 if the transport process is
recombination in the depletion region). Typical variations of total current I
in both the dark and the light as a function of are given in Fig. 1.5. If the
voltage is zero (short-circuit condition), then of course there is zero current in
the dark, but in the light we have
and the short-circuit current is controlled only by the photoinduced current

generation and the recombination processes. If the total current under
Fig. 1.5. Typical idealized total light and dark current versus voltage curves for a photovoltaic
cell in which the principal cell parameters do not depend on photoexcitation, showing the
open-circuit voltage &, the short-circuit current I,,, and the maximum power point P,.
(Reprinted with permission from A. L. Fahrenbruch and R. H. Bube, Fundamentals of Solar
Cells: Photovoltaic Solar Energy Conversion, Copyright 1983, Academic Press, Orlando,
FL.)
illumination is zero (open-circuit condition), then solution of Eq. (1.1) for J = 0

gives
4oc = (AkT/q) ln[(JLIJo) 11 + (1.3)
Thus the open-circuit voltage is controlled by the current generation and re-
combination processes, but also by the nature of the junction transport currents
depending on A and J,. Combination of Eqs. (1.2) and (1.3) shows that the
relation between Jscand &,c is given by
Jsc = Jo[exp(PPoc/AkT) - 11 (1.4)

which is exactly similar to Eq. (1.1) for J versus 4 in the dark for this ideal
junction device. The equivalence of these two dependences is a basic test for the
absence of any light-related changes in the parameters entering the equations.
Photovoltaic Eficiency
Since photovoltaic efficiency is of central importance, we see next how this
efficiency is expressed in terms of this simple model. The efficiency of a pho-
tovoltaic solar cell is a maximum when the product of the current density J
and the voltage 4 is a maximum. The efficiency 17 itself can be expressed as
7 = P m / P r a d = Jmd’m/Prad = Jsc4oc.f f /Prad (1.5)

where P r a d is the total radiation power incident on the cell, and f f is called
the fill factor; f f is a measure of the “squareness” of the light J-4 curve, as
shown in Fig. 1.5. J , and 4m are respectively the values of current density
and voltage at the condition corresponding t o maximum power. The definition
of the fill factor ff can be obtained from Eq. (1.5),
ff = Jm4mf Jsc4oc (1.6)

The value of q5m can be obtained by multiplying Eq. (1.1)by 4 and maximizing
the power with respect to 4 .
4m = 4oc - ( A k T / q )l n [ ( q h / A k T ) + 11 (1.7)
which can be solved iteratively for 4m. Once a value for 4 , has been obtained,
the value of J,, and hence the maximum power P, = J,&, can be obtained
from Eq. (1.1) by substituting 4 = 4,. The fill factor for a junction describable
by Eq. (1.4) is a function of A and &, increasing with decreasing A and
increasing 4oc (Lindmayer, 1972).
Figure 1.6 gives general insights into the factors that determine the ef-
ficiency in an actual photovoltaic solar cell. The figure shows the various
components to the loss of efficiency in a standard single-crystal silicon cell for
irradiation by sunlight. Specific numbers depend, of course, on the details of
the material and the solar cell, and those given here are intended to be pri-
marily illustrative. The analysis is similar t o that carried out by Wolf (1971).
Starting from the top of the diagram down:
(1) Some of the cell area is obscured by the current-collecting grid, thus re-
ducing the effective cell area: 4% loss;
(2) some of the incident photons are reflected and not absorbed: 2% loss;
(3) some of the photons are absorbed in spurious absorption processes such as
at antireflection coatings, at defects, etc., which do not lead to free carriers:
1%loss;
G R I D COVERAGE 4.0%
hv < E 18.8%
SPURI(XIS ABSORmION 1 .O% 9
hv > E 29.2%
4
n Q = 0.90 4.5%
Eg ' ,¶" 19.2%
f f = 0.78 4.7%
nS 16.m
Fig. 1.6. Power loss chart for a silicon cell showing the percentage of total input power Prad
lost to each of the loss mechanisms. Values of J, = 5 x A cm-2 and A = 1 are assumed.
(Reprinted with permission from A. L. Fahrenbruch and R. H. Bube, Fundamentals of Solar
Cells: Photovoltaic Solar Energy Conversion, Copyright 1983, Academic Press, Orlando,
FL.)
(4) some of the incident photons have a n energy less than the band gap of the
semiconductor (hv < Eg), and hence have insufficient energy to produce
free carriers in the absorbing material: 18.8% loss;
(5) some of the absorbed photons have a n energy larger than the band gap
Eg of the absorbing material; the excess energy (hv - E g ) is non-usefully
dissipated in producing hot carriers which transform the light energy to
heat as the carriers thermalize to near the band edge: 29.2% loss;
(6) not every photoexcited free carrier is collected by the internal electric field;
this is expressed by the quantum efficiency VQ < 1: if V Q = 0.90, this
amounts to a 4.5% loss;
(7) in general the band gap Eg > qq50c, i.e., the energy used to create the
free carriers (hv 2 Eg)is greater than the energy associated with the
open-circuit voltage, and there is therefore an energy loss of 19.2%;
(8) finally in a real solar cell forward-biased t o q5m, with finite R, and R,, the
fill factor f f < 1: if ff = 0.78, this amounts to a 4.7% loss.
Given the various estimates listed here, the cell efficiency is finally 16.6%.
Losses (1) to (3), and (6) to (8), can be reduced by careful material control
and cell design. Losses (4) and ( 5 ) are difficult to avoid with simple solar cells,
but more complicated structures (graded gap or multijunction structures) can
be designed to help here as well. Photovoltaic cells with efficiency over 30%
have been designed and produced.
Summary of Important Materials Properties

We now summarize the most significant materials properties that are important
for the preparation of high efficiency photovoltaic solar cells. Rothwarf (1987)
has listed some twenty to thirty materials and processing related parameters
that must be controlled and optimized for maximizing solar-cell performance.
(1) Band gap of the absorbing material. The band gap of the absorbing ma-
terial must be small enough to allow absorption of an appreciable portion
of the solar spectrum, and at the same time large enough to minimize the
reverse saturation junction current density J,.
(2) Diffusion length of minority carriers. The diffusion length of minority car-
riers must be as large as possible so that carriers excited by light some
distance from the actual semiconductor junction will be able to diffuse to
the junction and be collected before they recombine with carriers of the
opposite sign. The diffusion length of minority carriers L m i n is given by
L m i n = (Drnin7min)1’2 = [ ( l c T / q ) ( ~ 7 ) , i n ] ~ / ~ , where D m i n is the diffusion
constant, 7,in is the lifetime, and p,in is the mobility, for minority carriers.
It is desired, therefore, to have a material in which the minority carriers
have as large a mobility and lifetime as can be obtained. The value of the
mobility is more or less determined by the choice of material and does not
vary over a wide range. The value of the lifetime, however, is very sensitive
to a variety of phenomena in the bulk and a t the surface that contribute to
recombination of photoexcited carriers. Optimization of efficiency must in-
clude solar cell growth and deposition conditions that maximize the minor-
ity carrier lifetime. Cell design must include photoexcitation of minority
carriers within a diffusion length of the collecting junction.
( 3 ) Desirable junction properties. The actual junction structure and compo-
sition determines the magnitude of the junction transport current density
J , and of the ideality factor A . Formation of the semiconductor junction
must be carefully controlled, therefore, t o produce junctions with as low a
junction current as possible. Various typical mechanisms for the junction
current are summarized in Sec. 1.4.
(4) In the simple analysis of this section, we have assumed that R, = 0 and
R, = 00 in Fig. 1.4. In real solar cells, however, finite values of these
two resistances will be present and can be a major factor, particularly in
determining the effective value of the fill factor ff. Contributions to the
series resistance R, can arise both from the resistance of the semiconductor
bulk and from the contact resistance to the semiconductor t o complete the
circuit. Problems involving semiconductor doping and control of contact
resistance can play a significant role in some cases. The parallel resistance
R, can be reduced by grain boundaries or other defects that enhance for-
ward junction current and contribute t o an increase in J , and a decrease
in &,=. In polycrystalline thin film solar cells, grain boundaries at the
junction interface can critically affect junction transport properties.
(5) Solar cells are intended for use in exposed areas for long periods of time
without failure. This means that a variety of phenomena that might lead
to a decrease in cell efficiency with time of exposure must be carefully
considered. In some cases, as we shall see, these instability problems may
play a dominant role in determining cell efficiency and utility.
All five of these areas of materials properties must be carefully designed

and controlled to maximize the efficiency of an actual solar cell. One of the
purposes of this book is to describe the ways in which practical considerations
of this type have been considered and dealt with.
Reference Information
This book provides three kinds of reference information at the end of the vol-
ume: (1) a representative bibliography of books that have been written on the
subject of photovoltaics, with entries listed chronologically; (2) a representa-
tive list of review papers on aspects of photovoltaics, with entries also listed
chronologically; and (3) a traditional list of references to specific research re-
ferred to throughout the book by name of author and date of publication, listed
alphabetically by first author’s name.
In addition, general attention should be called to the published papers pre-
sented at a number of meetings dedicated to the subject of photovoltaics. The
proceedings of the IEEE Photovoltaic Specialists Conference, with meetings
held at 18 month intervals and its 25th meeting in May 1996, are a rich source
of information on progress in the field. At this 25th meeting, for example,
370 papers were presented involving almost 1000 authors. The first World
Conference on Photovoltaic Energy Conversion met in Hawaii as part of the
24th IEEE Photovoltaic Specialists Conference in 1994, and the Second World
Conference is being held in Vienna in July 1998. There are comparable pro-
ceedings of the Photovoltaic Solar Energy Conferences of the Commission of
the European Communities; the 14th Conference was held in Barcelona in July
1997.
Another valuable source of continuing input is available through the Pro-
gram Review Proceedings and the Annual Reports published through the
years by NSF-RANN (1973-1975), ERDA (1975-1978), and DOE, and the
Solar Energy Research Institute (SERI), now the National Renewable En-
ergy Laboratory (NREL) (since 1978). The Office of Scientific and Tech-
nical Information of DOE also published a bimonthly collection of Current
Abstracts in Photovoltaic Energy. In 1996 this service was replaced by a
listing of abstracts on photovoltaic technology on the World Wide Web at:
http://www.doe.gov/phv/phvhome.html.Beginning in October 1996, it also
became possible to receive a listing of the citations to photovoltaic reports
processed by the Office of Scientific and Technical Information (OSTI) during
the preceding two months, by regular mail, e-mail, or fax.
Some of the background material included in the book, particularly in this
first chapter, is adapted with minor revision from the chapter by the author
on “Solar Cells”, in Handbook o n Semiconductors, Device Physics, Vol. 4, ed.
C. Hilsum, 797-839 (1993), with kind permission from Elsevier Science, NL,
Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands. Consid-
erable use has also been made of two other books involving the author for
background material and insights into earlier years of research on photovoltaics:
Fundamentals of Solar Cells: Photovoltaic Solar Energy Conversion by
A. L. Fahrenbruch and R. H. Bube, Academic Press, N.Y. (1983), and a chap-
ter on “Photovoltaic Effects” in Photoelectronic Properties of Semiconductors
by R. H. Bube, Cambridge Univ. Press, Cambridge (1992).
1.2. Applications of Photovoltaics

Photovoltaics are primarily devices to provide alternative sources of electrical
energy using the radiant energy that comes to us from the sun. Most of these
attempts are motivated by the realization of the limited supply of fossil fuels,
the undesirable consequences of nuclear fission, and the stress that energy
supply places on the environment in a world with a growing population, a
relatively small fraction of which uses far more than its proportional share
of energy a t the expense of the rest. If the future of the earth is considered
in terms of hundreds, rather than tens of years, traditional sources of energy,
such as coal, oil and natural gas, provide only a limited resource. Furthermore,
growing usage of these fossil fuels contributes to a variety of environmental
problems: air pollution, acid rain, and the greenhouse effect, to name only a
few. In principle nuclear energy might be considered as a way to overcome
these problems, but nuclear fission is a n uninviting prospect in view of the
dangers in plant safety, waste disposal, unfavorable economics, and potential
for misuse, and nuclear fusion is still an uncertain possibility.
The utility of photovoltaics is especially significant with respect to remote
applications, and one of the chief advantages of photovoltaics in the future
is decentralization of the power grid, a consideration also related to remote
energy use.
A Fundamental Limitation
It should be remembered that there is a fundamental thermodynamic con-
straint on our ability to convert energy on earth, considering the accompany-
ing heat, without catastrophic effects. If we were to release on earth, through
the use of either fossil fuels or nuclear energy, heat corresponding to 1% of
the solar power density falling on the earth averaged over a year, the average
temperature of the earth would be increased by about 1"C, with major effects
on climatic conditions all over the world. Today the average level of energy
density consumption in the United States is already about 0.2% of the incident
solar power density, with considerably higher values in urban areas. Only re-
newable energy sources such as solar and wind energy enable us to avoid these
constraints.
What Photovoltaic Energy is Available?

Is photovoltaic use of solar energy adequate to the task? Sunlight falls on the
earth with an intensity of about 1 kW/m2. If this energy could be converted to
electricity with a relatively modest 10% overall efficiency, 1 kW of electricity
would be generated for every 10 m2 of active area as long as the sun was
shining near its peak intensity. This is of the order of the average electricity
usage per residence. Because the sun does not shine a t its peak intensity for
24 hours on any day, and because the periods of sunny days are interspersed
with periods of cloudy days, both a greater area than this 10 m2 (by a factor
of about ten) and a means of electrical storage are required to distribute the
use over non-sunny periods.
Main Areas of Concern f o r Photovoltaics

The basic concerns for long-range use of photovoltaics for terrestrial solar en-
ergy conversion lie in three areas: (1) efficiency, (2) cost, and (3) operating
lifetime. These three areas are interrelated in a complex way. Already for a
number of years photovoltaics have been applied to a variety of localized tasks,
such as pumping water or telephone communications, in developing nations or
elsewhere in the world where a power grid does not currently exist. It is the
major use of photovoltaics to supply an appreciable fraction of the electrical
power on a general basis that raises critical issues.
(1) The achievable efficiency with a particular photovoltaic system is highly

important and it has become generally agreed that cell efficiencies of about
20% (increased from an earlier estimate of 10%) is a lower limit for large-
scale power applications. Even if cells with appreciably lower efficiency are
very inexpensive, the cost of the cell then becomes insignificant compared
to the costs of the installation required for its use. Contemporary effi-
ciencies range from about 14% for single-junction t hin-film polycrystalline
cells, to close t o 30% for single-junction single-crystal cells t o be used with
solar concentration (up to a factor of 1000 or more). Efficiencies greater
than 30% have been achieved with multijunction cells, devices in which
the sunlight is passed sequentially through two or more single-junction
cells to maximize the match between sunlight absorbed and semiconduc-
tor band gap. Most of these cells are made with either silicon (Si) or
111-V compounds related to gallium arsenide (GaAs). Only three ma-
terials used in single-junction thin-film cells without solar concentration
have been demonstrated to provide an efficiency greater than 10%: hy-
drogenated amorphous silicon (a-Si : H), cadmium telluride (CdTe), and
copper indium diselenide (CuInSez). Each of these major materials has a
chapter devoted t o it in this book.
(2) The basic cost of photovoltaic systems decreased dramatically by a factor
of twenty between 1956 and 1976, and in the last decade it has decreased
from fifteen dollars to 30 cents per kilowatt-hour; the cost goal by the end
of the next decade is six cents per kilowatt-hour. Photovoltaic cells for
terrestrial applications will take one of two major forms: a large-area, thin-
film, flat-plate form, probably installed at a fixed angle with respect to the
earth, suitable for large-area dispersed applications on rooftops etc., or a
single-crystal form to be used with a concentrator system built to maintain
maximum sunlight on the cell throughout the day through tracking of the
concentrator, for centralized power production. Reduction of cost for the
thin-film cells is achieved by minimization of the amount of material used,
the possibility of inexpensive materials processing methods, and the use of
inexpensive mountings. The single crystal cells are themselves generally
highly complex and expensive, but the small amount of material needed
with intense concentration of sunlight again effects a cost reduction.
(3) To be effective as an alternative energy source, a solar cell must generate at
least enough energy in its operating lifetime to pay back both the financial
and energy costs required to produce the cell in the first place, and hope-
fully several times this. It is estimated that an operating lifetime of about
20 years would be a workable value. This lifetime may be determined by
a variety of external factors such as physical damage, corrosion, deteriora-
tion of cell support structures etc., or by what is of more direct concern to
us in this book, by a variety of internal materials-related factors such as
diffusion, photogeneration of defects etc. For cells in space, as compared to
terrestrial-use cells, radiation damage is also a major factor in degrading
performance.
The Illustrative Case of Cu,S/CdS Solar Cells

Stability for long-term operation has proven to be a real problem for several
thin-film technologies. The original all-thin-film, solar cell system consisting
of a junction between Cu,S and CdS showed promise of reasonable efficiency
and ease of preparation (Reynolds et al., 1954; Boer and Meakin, 1975; Stan-
ley, 1975; Rothwarf and Barnett, 1977; Barnett, 1977). For a period of al-
most 20 years, dating from the late ' ~ O S , this photovoltaic system was the
only all-film cell available. Solar cells with 10% efficiency were also made with
Cu,S/Cdl-,Zn,S thin films (y = 0.10, 0.16) with open-circuit voltages greater
than that in Cu,S/CdS cells (Hall et al., 1981). A review is given in Fahren-
bruch and Bube (1983) and by Hill and Meakin (1985). Although commonly
prepared by the procedure of simply dipping CdS into a warm solution of
cuprous ions to effect a replacement reaction in which Cu,S forms topotaxi-
ally on the CdS, other methods of depositing the Cu,S were also investigated,
such as the vacuum evaporation of CuCl followed by heat treatment, or the
deposition of Cu,S by reactive sputtering.
The complexity of this system arises from the variety of Cu,S phases that
may exist at room temperature with quite different photovoltaic properties,
and from the ability to change from one phase to another during cell opera-
tion due to interaction with the atmosphere or diffusion of Cu into the CdS.
Cu,S can exist in the chalcocite phase (x = 1.995-2.000), which has superior
photovoltaic properties, the djurleite phase (x = 1.96), and the digenite phase
(x = 1.8) Reduction in the value of x can occur by diffusion of Cu into the CdS
or by oxidation of Cu a t the free surface of Cu,S, and results in a degradation

of photovoltaic properties. Any heat treatment of the cell causes appreciable
Cu diffusion into the CdS, which forms deep acceptor states in the CdS that
widen the depletion layer and lead to greater carrier recombination before col-
lection, giving rise to enhanced (narrow depletion layer), and quenched (wide
depletion layer) conditions. In addition to these effects, a n optical degrada-
tion process occurs through a reversible photoinduced defect reaction (Redfield
and Bube, 1996), caused by photoexcitation after Cu diffusion into the CdS
has occurred (Kanev e t al., 1969, 1971). This leads to a state where lifetime-
killing defects have been formed that can be thermally annealed away, giving
rise to degraded (lifetime killer defects formed), and restored (lifetime-killer
defects annealed away) conditions. In an appropriately heat-treated junction
of this type, the value of J,, for the enhanced and restored state (narrow de-
pletion layer and photoinduced defects annealed away), can be over lo3 times
that for the quenched and degraded state (wide depletion layer and photoin-
duced defects active). The effects associated with the diffusion of Cu into the
CdS upon heat treatment used in cell preparation, have been investigated for
Cu,S formed on single crystal CdS (Gill and Bube, 1970; Lindquist and Bube,
1972a,b). Detailed summaries of the results have been described (Fahrenbruch
and Bube, 1974, 1983; Bube, 1992).
Many attempts to produce a stable cell in spite of these problems looked
promising but proved unsuccessful and further work on the system was finally
abandoned, and we will not discuss the details of this particular system further
in this book. We refer the interested reader to the above discussions in the
literature for what is scientifically a fascinating problem. Among today’s thin-
film cell materials, stability is a special problem for a-Si:H cells because light-
induced formation of defects decreases the lifetime and diffusion length of free
carriers; this particular problem remains a live issue and is discussed in more
detail in Chapter 3.
1.3. Types of Semiconductor Junctions

There are six different types of semiconductor junctions that have possible
application in photovoltaic solar cells, each junction having the fundamental
role of supplying the internal electric field needed to separate the photoex-
cited carriers and to cause them to flow as a current in the external circuit:
(1) homojunctions, (2) heterojunctions, (3) heteroface junctions or buried ho-
mojunctions, (4) metal-semiconductor junctions (Schottky barriers), ( 5 ) p-
i-n junctions, and (6) semiconductor-electrolyte junctions. We describe the
characteristic energy-band structure for each of these junctions in this section.

Discussion of the use of different materials in these possible junction config-
urations for photovoltaic solar energy conversion makes up the rest of this
book.
Homojunc tions
A typical energy-band diagram for a homojunction is given in Fig. 1.7. A
homojunction consists of a junction between two portions of the same semi-
conductor, one doped p t y p e and the other doped n-type, hence the name, p-n
junction. Typical details of such an energy-band diagram are shown in the fig-
ure: the vacuum level E,,,, the conduction band edge E,, the Fermi level E F ,
the valence band edge E,, the band gap E c , the electron affinity xs,and the
diffusion potential 4 4 0 . The work function q&v of a semiconductor is defined
as the energy difference (E,,, - E F ) . Since the work function of the p t y p e
portion of the material is greater than that of the n-type portion in Fig. 1.7,
-1
Ec i
\ 1 Eo
XI
0- - 0
Fig. 1.7. Energy-band diagram for a p n homojunction with equal densities of doping in the
p and n-type portions.
(q4wp- q4wn) = 440, the energy bands between p and n-type portions are
curved, indicating the presence of an internal electric field. Physically one can
think of the diffusion potential q$D as resulting from a transfer of electrons
from n-type to p t y p e material in order to equalize the Fermi energy on both
sides when the junction was formed, giving rise to a positive charge of ionized
donors in an electron-depleted layer near the junction interface on the n-type
side and a negative charge of ionized acceptors in a hole-depleted layer near the
junction interface on the p t y p e side, resulting in a flat Fermi level across the
whole structure. The diagram shown in Fig. 1.7 is specifically for the situation
where the doping of the p and n-type regions is the same, resulting in equal
widths for the depletion layers on both sides of the junction.
Photoexcitation produces free minority carrier electrons in the p t y p e re-
gion, and free minority carrier holes in the n-type region. Each of these then
diffuse toward the junction, and if they reach the junction without being re-
moved by recombination, they pass over the junction, are collected by the
junction field, diffuse through the other portion of the semiconductor and pass
into the external circuit. Since carriers must be excited within by about a
diffusion length of the junction in order to be able t o diffuse to the junction
before recombination occurs, the geometry shown in the insert in Fig. 1.7 is
frequently used, with the portion of the semiconductor on the illuminated side
being much thinner than that on the opposite side. If the semiconductor has
the high optical absorption characteristic of a direct band gap, then the illu-
minated side of the junction must be very thin (= 0.1 pm) t o allow light to
penetrate to within a diffusion length of the junction, but this has the disad-
vantage of causing many carriers to be generated near the surface where the
probability of recombination due to surface defects is greater than that in the
bulk. On the other hand if the semiconductor has a lower optical absorption
characteristic of an indirect band gap, then the portion of the semiconductor
on the opposite side to that illuminated must be quite thick to allow most of
the light to be absorbed, but then much of this absorption occurs more than
a diffusion length away from the junction unless the diffusion length of the
material is large. These considerations show immediately the need for a high-
quality, well-engineered material to serve in an efficient p n homojunction type
of solar cell. High-efficiency, single crystal Si solar cells are usually of the p n
homojunction type.
Heterojunctions
A p n heterojunction is a p n junction formed between two different semi-
conductors with different band gaps and electron affinities. A typical band
/Front-wall U B a c k - w a l l 1
1 \n
J
P-‘YPe n-‘Y pc
Fig. 1.8. Energy-band diagram for a p n heterojunction with equal densities of doping in
the p and n-type portions, and a choice of material parameters (XI < x 2 , E G <
~ E G 2 ) such
that there are no energy spikes at the junction interface.
diagram for a p-n heterojunction is given in Fig. 1.8, where the p t y p e material
is assumed to have a smaller band gap E G than ~ that of the n-type material
E G ~ As
. in Fig. 1.7, the assumption is made that the doping is of the same
magnitude for both p and n-type materials, giving equal-width depletion layers
on both sides of the junction.
A variety of complex phenomena can occur at the junction interface in such
a heterojunction, which we have simplified in Fig. 1.8, following the Anderson
abrupt-junction model (Anderson, 1962). In this approach we neglect any
effects of interface dipoles or interface states, and recognize that differences
between the electron affinities and band gaps of the two material give rise
to discontinuities A E , in the conduction band and A E , in the valence band,
which can in principle be either positive or negative. Figure 1.8 has been drawn
with the desirable assumption that x1 < ~ 2 so, that an energy spike does not
occur in the conduction band impeding electron transport from the p to the
n-type material.
As indicated in the insert in Fig. 1.8, photoexcitation could be either
on the n-type material (back-wall) or on the p t y p e material (front-wall).
Back-wall excitation profits from the larger band gap of the n-type material,
which acts essentially like a window even for light that is highly absorbed in the
p t y p e region, and allows the light to penetrate through to the junction with
minimum loss. On the ot,her hand, other problems are introduced which are
related t o the likelihood of lattice mismatch at the junction between the two
semiconductors, and which may in itself produce localized interface states that
facilitate carrier loss through recombination at what is now a kind of “internal
surface”. Such localized interface states may also play a role in increasing the
reverse saturation current density Jo and hence reducing &.
A typical summary of design choices for materials to be used in a hetero-
junction is given in Table 1.1.
Table 1.1. Material considerations for use in a heterojunction solar cell.
Property Criteria
Band gap of smaller band-gap material Direct gap near 1.4 eV

Band gap of larger band-gap material As large as possible while maintaining low series
resistance
Conductivity type Smaller band-gap material should be p t y p e be-
cause of longer electron diffusion lengths
Electron affinities Such that no potential spike occurs at the junc-
tion for minority carriers
Diffusion voltage, 4~ Large, since maximum +oc 0: +D
Diffusion length Long electron diffusion length in p t y p e material

Lattice mismatch Small as possible to avoid interface states at the
junction
Electrical contacts Low-resistance contacts to both n- and p t y p e
materials
Material availability Good supply of material available
Material cost Material costs must be competitive
Material toxicity Materials should be non-toxic, or possible effec-
tive control of toxicity
Cell stability Materials should be free of interactions leading to
changes in properties with time or operation
Sometimes a variation on the p n heterojunction between two semiconduc-

tors (sometimes called an SS junction, where ‘S’ stands for ‘semiconductor’)
is made by including a thin layer of an insulating material between the two
semiconductors (to form an SIS junction) to help reduce the junction currents
that decrease &=.
Buried Homojunctions or Heteroface Junctions

The energy band diagram of Fig. 1.9 pictures what is called a “buried homo-
junction” or a “heteroface junction”. It is an effort to benefit from the best
properties of a homojunction and a heterojunction, while minimizing their
problems. The structure shown consists of a large band gap p+-type material
which forms a heterojunction to a smaller band gap p t y p e material, which
in turn forms a homojunction with an n-type material with the same band
gap. The primary purpose of the structure is to decrease losses due to surface
recombination at the illuminated surface in the homojunction configuration by
providing the p+-p junction with good lattice matching. One of the most suc-
cessful developments of this type is the p-GaAlAs/pGaAs/n-GaAs cell (Hovel
et al., 1972; MacMillan et al., 1988), for which the lattice constant of AlAs is
0.5661 nm and that of GaAs 0.5654 nm; the proportion of A1 in the GaAlAs
P+
Fig. 1.9. Energy-band diagram for a p+-p-n buried homojunction or heteroface junction in
which the pf material acts as a large band gap window and a n ohmic contact to the p t y p e
material. Inset shows the typical direction of illumination for use as a solar cell.
solid solution compound is chosen to provide (a) a large enough band gap to act
as a window layer for solar energy, and (b) a good lattice match to the GaAs,
hence providing a low interface-recombination velocity at the p'-p interface.
Schottky Barriers
The previous three types of photovoltaic junctions all involve junctions between
two semiconductors. A conceptually simpler junction can be obtained from a
Schottky barrier metal contact to a semiconductor (an MS junction).
I I
Semi-
conductor
Metal
n-type semiconductor
Fig. 1.10. Energy-band diagram for a Schottky barrier metal contact t o a n n-type semicon-
ductor, based on the energy parameters of the materials without including interface effects.
A typical energy band diagram for a Schottky barrier on an n-type ma-

terial is given in Fig. 1.10. In the case shown, q 4 >
~ q4s, and upon con-
tact electrons flow from the n-type semiconductor t o the metal, causing a de-
pletion layer in the n-type semiconductor and an internal electric field next
to the junction, which is able to collect photoexcited carriers and enable
them to contribute to electric current in a n external circuit. [For a p t y p e
semiconductor, a Schottky barrier is formed if qc$M < q@s,and holes flow

from the semiconductor to the metal upon contact, causing a depletion layer
for holes next t o the junction.] Although a simple approach equates the dif-
fusion potential of the Schottky barrier to the difference between the work
functions of the metal and the semiconductor ( q $ D = Qc$M - q$s), many more
complex interactions can occur a t the interface that cause variations from such
a prediction (e.g. see Fahrenbruch and Bube, 1983). The actual height of a
specific Schottky barrier must often be determined experimentally.
Analogous to the case of the SS and SIS junctions, it is frequently found
desirable to insert a thin layer of insulator in a Schottky barrier junction to
reduce J,, forming a n MIS junction, sometimes referred to as a n MOS junc-
tion if the insulator is an oxide (Anderson et al., 1977; Stirn and Yeh, 1977).
Suitable energy band structures can exist so that the insulator layer reduces
the leakage currents of the Schottky barrier, and, as long as it is thin enough
not to impede carrier collection, can contribute to improved cell performance.
p-i-n J u n c t i o n s
What we refer to here as a p i - n junction (see Fig. 3.15 f9r the energy band
diagram of a pi-n junction for a-Si:H) differs from the SIS junction mentioned
above in two major ways: (1) the insulator in an SIS or MIS junction is a
thin layer confined to the junction region, whereas the insulator in a p i - n
junction is usually a thick undoped layer of the same semiconductor where
the principal absorption of light occurs; and (2) transport of carriers in an
SIS or MIS junction occurs by diffusion between the depletion layer and the
contacts, whereas transport in a p i - n junction occurs by drift under a n electric
field that exists throughout the insulator. Since a collecting electric field exists
throughout t,he region where free carriers are being formed by photoexcitation,
there are definite advantages to the p i - n structure. It becomes possible, for
example, to use a semiconductor with desirable properties of other kinds but
with a diffusion length too small to be useful in a conventional p n structure.
One of the most efficient developments in crystalline silicon solar cells is the
p i - n back point-contact (BPC) cell (Swanson et al., 1984) which is discussed
in Sec. 2.4. a-Si:H solar cells are usually fabricated in the form of a p i - n
junction (Carlson, 1977). An example of a heterojunction p i - n structure is
the n-CdS/i-CdTelpZnTe solar cell (Meyers, 1989). Here an n-CdS layer is
deposited on SnOz-coated glass, an i-CdTe layer is deposited by electrodepo-
sition on the CdS, and a p Z n T e layer is deposited on the CdTe.
Photoelectrochemical Cells
The sixth type of junction goes back all the way to the first discovery of
the photovoltaic effect by observing what happens when a semiconductor-
electrolyte interface is illuminated. Two types of phenomena are of interest:
photoelectrolysis (Bocarsly et al., 1977) and photoelectrochemical cell per-
formance (Gerischer, 1975; Chai et al., 1977; Lewis, 1995). A typical band
diagram for photoelectrolysis is given in Fig. l . l l ( a ) , corresponding t o the
experimental arrangement shown in Fig. l . l l ( b ) , in which electron-hole pairs
are excited in a large band-gap semiconductor, which can then be used to dis-
sociate water. A photoelectrochemical arrangement is shown in Fig. l . l l ( c ) ,
involving an oxidation reaction associated with photoabsorption a t one surface
and a reduction reaction at another surface, providing a flow of electrons t o
the external circuit.
+ “2
I 0, + jH20
H’ //
2-
(b) (C)
Fig. 1.11. (a) Energy-band diagram for photo-electrolysis using a semiconductor; (b) ex-
perimental arrangement for photoelectrolysis using a semiconductor; (c) experimental setup
for a photoelectrochemical cell using a semiconductor. (Reprinted from R. H. Bube, “So-
lar Cells”, in Handbook on Semiconductors. Device Physics. Vol. 4C. C. Hilsum, ed., 1993,
p. 797, with kind permission from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV
Amsterdam, The Netherlands.)
1.4. More D e t a i l e d P h o t o v o l t a i c Models

As a first step from the idealized simple model treated in Sec. 1.1 to a more
realistic model of a photovoltaic cell, we turn our attention now to several ways
of introducing corrections and changes more descriptive of the actual situation.
Three major effects need to be included: (1) effects of R, > 0 and R, < 00
in Fig. 1.4, (2) voltage-dependent collection effects that make the actual light-
generated current density less than J L , and (3) the possibility of a change in
the major parameters J o , A , R, and R, between the dark and light conditions.
In the following description, some relatively simple approximations are made
to include the consequences of each of these effects.
Differences between Dark and Light Conditions

The single Eq. (1.1) for the junction current in the ideal case must be replaced
by two equations, one for the situation in the dark and the other for the
situation under photoexcitation. In the dark, we have
J d = yd{J,”exp [ad(4- J d R t ) ]+ 4/R,d - J,”}
where the superscript d denotes the dark condition, yd = 1/(1 + Rt/R,d),

ad = q/AdkT for transport mechanisms not involving tunneling, and ad = afd
for transport mechanisms involving tunneling (as described further below). In
the light, we have
where the superscript 1 denotes the light condition and other definitions are
similar to those in the dark. The function H ( 4 ) is a voltage-dependent collec-
tion function that describes what fraction of the light-generated carriers are
collected and contribute to the current; we may approximate H ( 4 ) as follows
(Fahrenbruch and Bube, 1974; Mitchell et al., 1977a, b ) .
Collection Function
For the sake of simplicity, consider a p-n heterojunction with a large band-gap
n-type material which transmits photons with energy less than its band gap
without loss to the p t y p e material where they are absorbed. The collection
function H ( 4 ) can be separated into two contributions:
Here g(4) describes the loss of carriers by recombination in the bulk of the
p t y p e material before they can diffuse to the junction to be collected, and
h ( 4 ) describes the loss of carriers by recombination due to interface states at
the junction interface. Qualitatively one would expect that g(4) will depend
strongly on the photon energy, decreasing for photon energies with lower optical
absorption, since carriers are freed further and further from the collecting
junction and have an increasing probability of recombining while diffusing to
that junction; and that h(4) will be relatively independent of photon energy
but will depend strongly on the electric field a t the interface.
The collection function g(4) can be calculated as follows:
(1.11)
The dependence of g(4) on the photon energy occurs through a(hv). The first
term in Eq. (1.11) describes the complete collection of all carriers created in the
depletion layer with width w, assuming that the drift field there assists in this
collection. The second term expresses the possibility of recombination loss of
such carriers with increasing distance from the depletion layer if the diffusion
length of electrons in the p t y p e material is L,. Integration of Eq. (1.11)gives
the following expression for g(4):
g(4) = 1 - exp[-aw(4)1/(1 +G J (1.12)

which depends on the variation of depletion layer width w with voltage 4,
w(4) = [2&&0 (4D - 4)/4"D+]"z (1.13)
where No+ is the density of ionized donors in the depletion layer. As w(4) > 0 ,
g(4) > 1/P + (1IaLn)l.
A simple expression for the collection function h(4) can be obtained by as-
suming that recombination at the interface is described by an interface recom-
bination velocity S I , and that the recombination probability can be considered
to be a simple competition between crossing the junction without recombina-
tion and recombination a t the interface:
h(4) = 1/(1+ s r / m (1.14)

where p is the mobility of carriers a t the interface, and E is the electric field
at the interface, given by E = 2(40 - 4)/w(4). If there are N I interface states
per square centimeter a t the interface with a capture coefficient of PI cm3 s-l,
then S I = NZPI cm s-'. The carrier velocity p E must be considered to have a
maximum value corresponding to the saturation of drift, velocity at high fields.
- 1 .O V Reverse
80
5
I
u
.-
V
E
5
J
40
d
20
0
0.50 0.60 0.70 0.80
Wavelength (pm)
Fig. 1.12. Spectral dependence of the quantum efficiency for a n n - C d S l p C d T e heterojunc-

tion, illustrating the contributions of collection function g(v) (decreasing with increasing
wavelength) and h(v) (increasing with applied reverse bias). (Reprinted with permission
from K . W. Mitchell e t al., J. A p p l . Phys. 48, 4365 (1977). Copyright 1977, American
Inst it ut e of Physics .)
An example of the qualitative effects of these collection functions is given

in Fig. 1.12, showing the spectral response of quantum efficiency (density
of electrons due to light in external circuit divided by density of p h o t o d
absorbed) in an n-CdSlpCdTe photovoltaic heterojunction (Mitchell et a!.,
197713). The short-wavelength cutoff of the spectral response is due to the
absorption of shorter wavelengths by the large band gap n-type CdS, while the
long-wavelength cutoff is due to failure of the small band gap p t y p e CdTe to
absorb longer wavelengths. The effect of the collection function g ( 4 ) is seen in
the negative slope of the quantum efficiency toward longer wavelengths, with
negligible dependence on voltage 4. The effect of the collection function h(4)
is seen in an increase in quantum efficiency with applied reverse bias (thus
increasing E a t the interface, and/or decreasing SI through its own voltage

dependence) with negligible dependence on wavelength. Experimental values
of h(4) = 0.84 a t 4 = 0 and h(4) = 0.89 at 4 = -1 V, indicate a relatively
large value of S I = 2 x lo6 cm s-', consistent with the fact that CdS and CdTe
have a large 9% lattice mismatch.
Other Photovoltaic Parameters

When the more realistic junction model of Eqs. (1.8) and (1.9) is considered,
the other photovoltaic parameters must also be recalculated. For example, the
open-circuit voltage becomes
4oc= (l/a')ln[H(4oc) (JL/JA) +1 - 4oc/JARk] (1.15)

and the short-circuit current density becomes
J,, = y L [ Jexp(-a'J,,R:)
i -A
J - H(O)JL] (1.16)
It can readily be shown that for the relationship between J,, and qhOc in this
more realistic situation to be the same as the relationship between Jd and 4
(as was the case in Eq. 1.4), requires seven conditions to be met: y, R,, a ,
and J , must all be independent of light; H ( 0 ) must be equal to H ( 4 0 c ) ;J d R i
must be much less than 4; and exp(-a'J,,R;) must be of order unity.
Junction Transport Processes

The parameters J,, and A play critical roles in determining the value of the
open-circuit voltage of a solar cell. Simple models of current transport through
the junction interface have been developed t o indicate some of the significant
factors that affect J,, and A in typical idealized cases, and to provide cri-
teria for deciding from experimental data which transport process is active.
For simplicity, we use an n+-p heterojunction ( N D > N A , E G < ~ E G ~for)
the following summary of these processes, and illustrate them qualitatively in
Fig. 1.13.
Diffusion
The mode of junction transport corresponding to the smallest values of J, and
to A = 1 corresponds to a diffusion-controlled current over the junction barrier
associated with the injection of electrons [Process (1) in Fig. 1.131 from the
n-type material into the p t y p e material. After injection and diffusion, recom-
bination finally occurs away from the junction in the p t y p e semiconductor
bulk. The current can be expressed as
ho 2 Recombination
Foward bias current transport

I
Fig. 1.13. The three major modes of forward junction current transport: (1) injection
over the barrier, (2) recombination in the depletion layer, and (3) tunneling, with or with-
out thermal assistance, through interface or imperfection states, followed by recombination.
(Reprinted from R. H. Bube and A . L. Fahrenbruch, “Photovoltaic Effect”, in Advances in
Electronics and Electron Physics 56, E. Marton, ed., p. 163. Copyright 1981, Academic
Press, Orlando FL.)
(1.17)
with a d i f f = q/kT and A = 1, and
where, in the p t y p e material, ni is the intrinsic carrier density, N A is the

density of acceptors, Ln is the electron diffusion length, and r, is the electron
lifetime. A plot of l n ( J o T 7 l 2 )versus 1/T has an activation energy of EQ,.
Recombination an depletion region

The second smallest mode of junction transport involves recombination in the
depletion region [Process (2) in Fig. 1.131. A recombination rate expression is
used based on Shockley-Read recombination (e.g. see Ch. 4 in Bube, 1992),
with integration across the depletion regions. The current can be expressed as
(1.19)
Jo - 4)lw
= qn,[1/(7,07,,)1/21[7TkT/4(4D (1.20)
where w is the depletion layer width, T ~ is , the minimum electron lifetime
when all recombination centers are empty, and r,, is the minimum hole lifetime
when all recombination centers are electron-occupied. The value of A has a
maximum value of 1.8 for symmetrically doped junctions if the levels at which
recombination occurs lie at mid-gap; otherwise values of A between 1 and 2
may correspond to this mechanism (Sah et al., 1957). A plot of In ( J O T p 5 / ' )
versus 1/T has an activation energy of E G , / ~ . For unsymmetrically doped
junctions, the value of A may be equal t o or larger than 2 (Choo, 1968).
Interface recombination without tunneling

At an n + p interface, the density of electrons is large and current is limited by
the availability of holes, which must overcome the barrier in the valence band.
Such currents may be described by
with aint= q/kT and A = 1. Two conditions may exist: (1) the thermal
velocity Zlth of the electrons is larger than the interface recombination velocity
s I , so that the current is limited by interfacial recombination, in which case
where SI is the electron capture cross-section of interface states with density

Nr, and a plot of l n J , versus 1/T has an activation energy of 440; or ( 2 )
the thermal velocity of an electron is smaller than S I , so that the current is
limited by the diffusion of holes to the interface, in which case J , follows the
expression for thermionic emission:
J , = A'T2exp(q4D/kT) = ( 4 7 ~ q m i / h ~ ) ( k exp(-q+D/kT)
T)~ (1.23)
and a plot of 1n(JOT-') versus 1/T has an activation energy of 440.
Tunneling limited recombination through interface states without

thermal assistance
Electrons from the n-type material descend through interface states and then
tunnel [Process (3) in Fig. 1.131 through the base of a barrier of height E b
into the valence band of the p t y p e material. A simple model for this process
involves tunneling a t the base of a parabolic barrier (Riben and Feucht, 1966).
The junction current in this case is
Jti = J,[exp(a/kT - 11 (1.24)
with a = (47r/h) ( & m * / N ~ )independent

l/~ of temperature, and
t 1/2
J, = qp(kT/m ) exp(-avo) (1.25)
so that a plot of 1n(J,T-'I2) versus a has an activation energy of 4 4 0 .
Thermally assisted tunneling through interface barrier

This model is similar to the last except that holes tunnel through the barrier
into electron-occupied interface states at a hole energy enhanced by thermal
excitation (Padovani and Stratton, 1966). The current is given by
Jtat = Jo[exp(a4) - 11 (1.26)
(1.27)
J,, = ({ 47rqm*( k T )'7r 1/2 E;L2 [q( - 4)]1 / 2 } / { h3k T C O S ~E,,

( /kT)
x [c~th(E,,,/kT]'/~))exp[-Efp(l/kT - l/E,)] (1.30)
with E, = E,, coth(E,,/kT). This model results in a n a that is weakly

temperature dependent. A plot of ln{Jo cosh(E,,/kT) [ ~ o t h ( E , , / k T ) ] ~ / ~ / T }
versus a has an activation energy of (q40 Efp). +
Tunneling processes commonly dominate junction currents in heterojunc-
tions, particularly in experimental systems and at lower temperatures. Exam-
ples of heterojunctions in which this model appears to appropriately describe
the data include n-CdS/p-Zno,3Cdo.7Te (Peters et al., 1988), ZnO/CdTe (Ara-

novich et al., 1980), and ZnO/InP (Eberspacher et al., 1984).
1.5. Photovoltaic Materials

The various chapter titles in the remainder of this book indicate the materials
that have played a major role in photovoltaic solar energy conversion. Single
crystal materials may be useful in high-technology, relatively expensive cells
to be used with concentration of sunlight. In single crystal form only Si,
GaAs, InP, CdTe and CuInSea can be used in photovoltaic devices to produce
efficiencies greater than 1096, and of these only Si and GaAs, and solid-solutions
based on them, are considered seriously for terrestrial applications.
This situation calls attention to the importance of thin-film technology in
producing thin-film photovoltaic cells for terrestrial applications. In thin-film
form, a-Si:H, CdTe and CuInSea are the leading candidates for solar-cell ap-
plications. The thin-film technology used must pay particular attention t o the
processing costs associated with large-area production. Not only are thin films
needed for the active solar cell layers themselves, they are also needed for win-
dow materials, anti-reflection coatings, passivating coatings, and transparent-
conducting contacts (e.g. CdS, ZnCdS, ZnO, SnO, Sn02, 111203, and indium-
tin oxide (ITO)). Decisions have been needed on whether to produce these films
by one of the standard methods such as vacuum evaporation, non-reactive or
reactive sputtering, electron-beam evaporation, molecular beam epitaxy, and
chemical vapor deposition, or by one of a set of developing techniques, such as
close-spaced vapor transport (Nicoll, 1963; Saraie et al., 1972; Yoshikawa and
Sakai, 1974; Buch et al., 1977), spray pyrolysis (Chamberlin and Skarman,
1966; Ma et al., 1977; Ma and Bube, 1977), and electrochemical deposition
or plating (Panicker et al., 1978). The references cited here indicate some of
the earlier investigative work; more recent work is described in the following
chapters. An assessment of polycrystalline thin films for solar cell applications
as of 1982 is summarized by Rothwarf (1982).
Because of the limited number of different materials, research has attemp-
ted to broaden the range of possible materials by focusing on solid solutions
between these and related materials: e.g. a-Si:C:H, a-Si:Ge:H, Cu,Agl-,InSen,
CuGa,Inl-,Se~, GaInP2, Zn,Cdl-,Te, and Mn,Cdl-,Te. Although in prin-
ciple it is possible to design “ideal” photovoltaic systems with ideal band gap
and no lattice mismatch at heterojunction interfaces, by resorting to more
complicated ternary, quaternary, pentenary, and even more complex systems,
the materials problems entering in these more complex systems appear to be
a serious limitation.
A major attempt a t increasing efficiency with the limited number of mate-

rials available has led to the development of multijunction cells, in which two
(or more) different cells are used together in series t o more efficiently absorb
the light. Although the measured efficiency for such a multijunction cell can
be expected to exceed that of either cell used separately, it is clear that effi-
ciencies do not simply add in such a multijunction cell, since only a fraction
of the incident light reaches the lower cell. The ideal situation would be to
use a large number of such cells in a multijunction such that each cell could
effectively absorb light only within a narrow range of its band gap. Examples
of early multijunction cells with two components, and the efficiencies achieved
are: GaAs/Si (31%) (Gee and Virshup, 1988); GaAs/CuInSez (21.3%) (Stan-
bery et d., 1977; Kim et al., 1988); AlGaAs/GaAs (24-28%) (Lewis et d.,
1988; Virshup et al., 1988; MacMillan et al., 1989); a-Si:H/CuInSeZ (15.6%)
(Mitchell et al., 1988); a-Si:H/a-Si:Ge:H (13.6%) (Guha 1989); GaInPz/GaAs
(25%) (Olson et al., 1989). As we shall see in our later discussions, the struc-
tural complexity of even these two-component multijunction cells is often not
trivial.
CHAPTER 2
CRYSTALLINE SILICON
2.1. Overview
Silicon has dominated most semiconductor applications for almost 50 years. It
is the second most abundant material of the earth’s crust, stable and non-toxic;
its technology is highly developed; and in its crystalline form it has an almost
ideal band gap for photovoltaic solar energy conversion. It is not surprising,
therefore, to find that silicon has been the dominant photovoltaic material
in solar cell applications over most of this time period. In 1981 the Si p-n
homojunction cell was the only solar cell widely available commercially.
“Polycrystalline” silicon is the historically generic name for all non-single-
crystalline silicon. In recent years, an effort has developed t o distinguish be-
tween different types of material on the basis of the size of the individual
single-crystal grains in the material, and to reserve the specific name “poly-
crystalline” for just one of them (Basore, 1994). A complete “family tree” for
silicon can therefore be listed as follows: (1) single crystal - just one grain
(> 10 cm) characterizes the whole material; (2) multicrystalline (mc-Si) -
there are a number of different grains in the material but the grain size is
relatively large, of the order of 1 mm to 10 cm; (3) polycrystalline - many
grains are present in the material with grain dimensions of the order of 1 pm
to 1 mm, as is also the case for polycrystalline films of CdTe (Chapter 5 ) or
CuInSez (Chapter 6); (4) microcrystalline (pc-Si) - single crystal regions in
grains can still be identified in x-ray diffraction patterns, but the grain size is
< 1 pm; (5) amorphous (a-Si) - no single-crystal regions identifiable by x-ray
diffraction occur since no long-range order is present. We discuss the varieties
of crystalline silicon in this chapter and amorphous silicon in Chapter 3.
The cost of single-crystal Si solar cells is greater than that of its closest
competitors, thin-film multicrystalline Si cells, and the impetus is often present
to trade the lower cost of the multicrystalline cells for the higher efficiency of
the single crystal cells. Single-crystal Si solar cells require very high material
quality; surfaces must be effectively passivated to reduce recombination there,
and the bulk properties must also be of high quality because of the long optical
penetration distances associated with the indirect band gap of Si. Specially
34
Crystalline Silicon 35
designed single-crystal Si solar cells have demonstrated efficiencies greater than

28% under concentrated sunlight, as described further below, while standard
single crystal Si solar cells have had an efficiency on the order of 15-17% (as
described in Fig. 1.6).
Most of the solar cells exhibited in various simple demonstrations or appli-
cations are actually multicrystalline silicon cells, and are visually identifiable
by the different reflection intensities from various grains in the material. Mul-
ticrystalline Si solar cells have been produced with efficiencies of about 17%,
and may be less expensively produced from somewhat less pure starting mate-
rials using less expensive manufacturing methods. It has been estimated that
single crystal efficiencies may ultimately reach 35%, while multicrystalline effi-
ciencies may ultimately reach 19% (Hubbard, 1989; Hubbard and Cook, 1989).
The procedure for the growth of single-crystal Si is summarized in Fahren-
bruch and Bube (1983), and the technology involved in the preparation of pure,
high-quality Si has continually improved (Ciszek, 1988). Silicon single crystals
have frequently been grown by one of two major growth methods (Matlock,
1979): (a) the Czochralski technique, in which a seed of known orientation is
dipped into a melt of silicon, the temperature is decreased slowly, and the seed
with subsequent growing crystal is pulled out of the melt, and (b) the float-zone
technique in which a narrow molten region is passed slowly along a Si ingot in
a vacuum or inert gas. Czochralski growth dominates the single-crystal solar
cell market.
Efficiency (Yo)
30
20
10
0
1940 1950 1960 1970 1980 1990 21 DO
Fig. 2.1. The increase in efficiency of single-crystal silicon laboratory solar cells. (Reprinted
with permission from M. A . Green, Szlicon Solar Cells: Advanced Principles & Practice,
Centre for Photovoltaic Devices and Systems, Univ. of New South Wales, Sydney, 1995.)
A developmental history, and a summary of principles and practice involved

in the production of Si solar cells are given by Green (1993a, 199313, 1995a),
whose summary of the rapid improvement in single crystal silicon solar cell
efficiencies is shown in Fig. 2.1. For each cell, the actual value of efficiency
for an AM1.5 spectrum a t 25°C and 1000 Wm-’ illumination intensity, the
type of cell structure used, the organization where the work was done, and a
relevant literature reference are given in Table 2.1.
2.2. Doping and Lifetime
Phosphorus and boron are the most widely used donor and acceptor dopants in
single-crystal Si. As the density of dopants is increased in the active absorbing
Table 2.1.
Date Eff. % Cell Structure Organization Reference
3/41 < 1% Melt-grown junction Bell Labs Ohl, 1941

3/52 1% He bombardment Bell Labs Kingsbury et al., 1952
12/53 4.5% Li diffused wraparound Bell Labs Pearson, 1985
1/54 6% B diffused wraparound Bell Labs Chapin et al., 1954
11/54 8% B diffused wraparound Bell Labs Bell Labs Record, 1954, 1955
5/55 11% B diffused wraparound Bell Labs Bell Labs Record, 1954, 1955
12/57 12.5% 0.5 x 2 cm B diffused Hoffman Elec. Green et al., 1992
8/59 14% Grid-contact B diffused Hoffman Elec. Green et al., 1992
8/61 15.2% B diff. A R coat, gridded Commercial, Mandelkorn et al., 1962
USASRDL
1/73 15.2% Violet cell Comsat Labs. Lindmayer et al., 1973
9/74 17.2% Textured non-reflecting Comsat Labs. Haynos et al., 1974
9/83 18.0% MINP cell UNSW* Green, 1991
12/83 18.3% PESC cell UNSW Green, 1991
5/85 19.0% PESC cell UNSW Green, 1991
10185 20.0% Microgrooved PESC cell UNSW Green, 1991
7/86 20.6% Microgrooved PESC cell UNSW Green, 1991
4/88 20.8% Microgrooved PESC cell UNSW Green, 1991
9/88 22.3% Rear point contact cell Stanford Univ. Verlinden et al., 1988
12/89 23.0% PERL cell UNSW Green, 1991
2/90 23.1% PERL cell UNSW Green, 1991
2/94 23.5% PERL cell UNSW Zhao et al., 1994
9/94 24.0% DLAR PERL cell UNSW Green e t al., 1995d
*The abbreviation UNSW stands for University of New South Wales, Australia.
layers of solar cells, two effects occur that degrade the electronic properties of
Si.
The lifetime is decreased both because of an increase in Shockley-Read type
recombination (electron-hole recombination through imperfections, giving up
the recombination energy as photons or phonons), and by the onset of Auger-
type recombination (in which the recombination energy is given up t o another
free carrier - see Sec. 2.4) for impurity densities in excess of 5 x 1017 cm-3
(Fischer and Pschunder, 1975; Redfield, 1978, 1979, 1980).
The carrier mobility, and hence the diffusion coefficient, is decreased be-
cause of an increase in charged impurity scattering, noticeable for impurity
densities greater than 10l6 ~ m - ~Accurate
. measurements of the mobility of
minority-carrier holes in phosphorus-doped silicon with doping in the lo1’
cm-3 range have been made using independent measurements of diffusion
length and minority-carrier lifetime t o obtain minority-carrier mobility values
(del Alamo et al., 1985; Swirhun et al., 1986; del Alamo et al., 1 9 8 7 ~ ) .Since
the absorber layer in the solar cell generally has doping of less than 10l6 ~ m - ~ ,
the mobility effect is usually negligible.
Deep-level impurities in Si may also decrease the lifetime of carriers through
recombination. Such impurities in roughly decreasing order of effect include
Ti, Zr, V, Na, Au, Cu, Fe, Mg, Cr , Mn and Ni, with tolerable densities varying
from 4 x 1013 cmP3 for T i t o 4 x 10l6 cm-3 for Ni (Hill et al., 1976; Davis
et al., 1980; Shimura, 1994). Particularly harmful are Na, Cu, and Fe since
they also have high diffusion coefficients in Si.
Introduction of dopants into the Si is usually by the process of diffusion,
which may be done in a variety of ways, often leading to a high concentration of
the dopant near the surface. This highly-doped layer has a decreased lifetime
and must be avoided or later removed in order not to have a “dead-layer” a t
the surface.
2.3. Major Sources of Recombination

Three major sources of recombination loss of photoexcited carriers in single
crystal Si solars cells exist: bulk, surface, and contact recombination.
Bulk Recombination
As described in Sec. 2.2, a major source of bulk recombination is associated
with imperfections in the bulk of the Si. The desired result is to minimize
recombination throughout the bulk through the use of high-quality pure Si
HCI, TCE
Contaminants
I Ep1 s1 I
I
Denuded
Zone . .
*. Intrinsic Gettering
.. .* dcfcclr
Silicon
p s s ,D e y
111 P dilluslon
poly-SI lilm Si,N, lilm Ion Implantation
f 1 Laser irradialion
Sand-blasling
Mechanical abrasion
I v J
I Extrinsic Gettering I
Fig. 2.2. Schematic illustration showing various gettering techniques for a silicon wafer
(Reprinted with permission from F. Shimura, Semiconductor Silicon CnJstal Technology,
Copyright 1989, Academic Press, Orlando, FL.)
starting material, thinning the bulk quasi-neutral regions, and limiting the
doping t o the minimum levels necessary t o achieve cell performance (Green,
1984).
This direct avoidance of impurities sometimes proves either too difficult or
too expensive, and other methods referred to as “gettering” are used to reduce
the impurity density in the bulk (Green, 1995a). These are shown schemati-
cally in Fig. 2.2 (Shimura, 1989). (a) A standard method in microelectronics
is “intrinsic gettering” which involves the formation of SiOz precipitates in the
bulk that act as gettering sites for further processing (Sardana, 1985) after de-
pletion of oxygen from the surface by out-diffusion at high temperatures. Since
this method results in very high quality material near the surface, but poor
quality material in the bulk, it is not suitable for photovoltaics. (b) A second
approach is “extrinsic gettering”, which involves the introduction of gettering

sites on one surface to which bulk defects diffuse upon high temperature treat-
ment. (c) A third approach is “chemical gettering” in which suitable chemicals
such as halogens are present in a gas stream over the crystal surface, where
they react with metallic impurities in the silicon to form volatile compounds
that leave the crystal.
In addition to these gettering techniques, there are also defect passivation
techniques in which a mobile species, such as atomic hydrogen, is incorporated
in the wafer, which can neutralize the electronic action of bulk defects (Sopori
et al., 1994).
Surface Recombination
Non-contacted areas of the surface of the Si provide locations where recombi-
nation is enhanced. This recombination is generally minimized by the growth
of a high-quality thermal oxide. The thickness of the oxide (14 nm to 80 nm)
does not appear to be an important parameter (Kopp e t al., 1992).
The magnitude of the effective surface recombination velocity Sefffor pho-
toinduced carriers at the Si-Si02 interface as a function of injection level has
been investigated (Aberle et al., 1992; Glunz et al., 1994a, 199413). A strong de-
pendence of Seffat the Si-SiOa interface on injection level and doping concen-
tration was found as shown in Fig. 2.3, which may be consistently interpreted
in the following way.
Results indicate that the electron capture cross-section of interface states is
much larger than their hole capture cross-section (Aberle et al., 1992). Because
of this difference in cross-sections, which makes the interface states behave sim-
ilarly to donors with a positive charge when unoccupied, the recombination
properties are quite different for n-type and p t y p e material. For n-type sur-
faces, there is a small density of holes near the surface, and hence the capture
of holes is the rate-determining recombination process; the net recombination
rate is small because of the small hole density and the small hole capture
cross-section. For p t y p e surfaces, however, the situation is more complex and
changes with increasing output voltage of the cell. At low voltages capture
of electrons is the rate-determining step, and the recombination process is
more effective than in p t y p e material because of the larger electron capture
cross-section. With increasing voltage across the cell, however, the situation
is reached where the hole capture becomes the rate-determining step, and the
effective surface recombination decreases, eventually t o values comparable to
1000,. I . I I I Ir I I
- 0.5 Rcm p-type

\, 1 R c m p-type
$.. 1 Rcm n-type
-< 100-
-
b,.
a 10 R c m p-type
E
0
W
-
~ 102...._.._._.._,.......
”’
N, =1.4x1Ol6 cm-’ -
- N, =7.5x101’ cm-’
-N, =6.5x101’ cm-’
.... ... .... N, =1.Ox1O1’c m - ’
I I I
1
Fig. 2.3. Measured injection dependence of the effective surface recombination velocity,
S,R, for differently doped silicon. (Reprinted with permission from S. W. Glunz et al.,
f Z t h European Photovoltaic Solar Energy Conference, p. 492 (1994). Copyright 1994, H. S.
Stephens and Associates, Bedford, United Kingdom.)
those found for n-type material. It must be kept in mind, however, that
specific fabrication details may be significant in determining the details of
surface recombination.
Recent developments in techniques for surface and bulk passivation are re-
ported by Loelgen (1995), who describes the effects of doped layers at the sur-
face on reducing the surface recombination, and of Al-gettering t o improve the
silicon bulk quality (Loelgen et al., 1994a,b);and by Leguijt (1995), who inves-
tigated the effects of surface passivation by low temperature plasma enhanced
chemical vapor deposition (PECVD) of silicon oxide or silicon nitride. Simi-
larly Rosmeulen et al. (1995) reported a 19.5% efficient solar cell passivated
by oxides deposited by low pressure chemical vapor deposition (LPCVD), and
Demesmaeker et al. (1994) reported promising results with low-temperature
surface passivation by means of a Tetra-Methyl-Cyclo-Tetra-Siloxane (TM-
CTS) LPCVD oxide.
Contact Area Recombination

The regions where metal contacts are made to the Si in the construction of a
solar cell to overcome the barrier to majority carrier transport, are likely to be
regions of high doping and hence of high recombination. One direct solution
is t o keep the contact area as small as possible. Another is t o strongly diffuse
these contact areas in order t o reduce the minority carrier densities in these
areas, with effectively the same results as a “back surface field” (BSF) (Loelgen
et al., 1993; Leguijt et al., 1995), such as is shown in Fig. 2.5. Other approaches
that have been investigated include the use of an MIS contact (Green and
Blakers, 1983) leading to an MINP (metal-insulator-NP junction) cell (Green
et al., 1984), which was the first silicon cell to demonstrate 18% efficiency;
semi-insulating polysilicon (SIPOS) contacts (Yablonovitch et al. , 1985); or
doped polycrystalline or amorphous silicon contacts (Lindholm et al., 1985).
2.4. Development of Single-Crystal Silicon Solar Cells

It is the principal purpose of this book to discuss the materials properties that
have been found to be significant for the design and construction of efficient
solar cells. Clearly the actual cell design and construction details themselves
play a major role in determining this efficiency. Although we include the sig-
nificant characteristics of the various types of cells and their major properties,
we do not intend to provide detailed information on cell design features them-
selves, and refer the reader to the bibliography and list of review papers at the
end of this text for more information of this type.
Typical Single Crystal Si Cell

The form of the first modern silicon cell is shown in Fig. 2.4(a), with the form
of the standard design in the ’60’s shown in Fig. 2.4(b). Typical single crystal
Si cells consist of a slice of crystal about 200 to 500 pm thick, although cells
with a thickness as small as 50-70 p m were early made with a n efficiency
of 12.5% using the Si available at that time period (Lindmayer and Wrigley,
1976; Chiang et al., 1978). On this p t y p e Si crystal, for which B is a common
acceptor impurity, an n-type layer about 0.1 to 0.5 pm thick is produced by
diffusion of P donors, typically from PH3. The energy band diagram for a
typical single crystal Si n+-pp+ cell is shown in Fig. 2.5 (for details of typical
cell fabrication, see Fahrenbruch and Bube, 1983).
The n-type layer is usually fairly heavily doped in order to decrease the
contribution of holes to the reverse saturation current J , when diffusion is the
(4
top metal finger antireflection coaling
/
n-type
/
rear metal
P-tYPe
IL
Fig. 2.4. (a) Form of the first modern silicon cell (Chapin et al. 1954); (b) standard design
for a space silicon cell (Mandelkorn et a!. 1962; Smith et al. 1963); (c) the shallow junction
“violet cell” (Lindrnayer and Allison, 1973). (Reprinted with permission from M. A. Green,
Szlzcon Solar Cells: Advanced Prznczples 0 Practzce, Centre for Photovoltaic Devices and
Systems, Univ. of New South Wales, Sydney, 1995.)
Fig. 2.5. Energy band diagram for a typical Si p+-n-nf solar cell with the n-layer thickness
exaggerated, and including a back surface field (BSF) created by A1 diffusion. (Reprinted
with permission from A. L. Fahrenbruch and R. H. Bube, Fundamentals of Solar Cells:
Photovoltaic Solar Energy Conversion, Copyright 1983, Academic Press, Orlando, FL.)
principal junction transport mechanism (see Eqs. 1.17 and 1.18). It was this
reasoning, leading to heavy doping of the n-type layer, that was responsible
for the long period of fairly flat solar cell efficiencies shown in Fig. 2.1. These
earlier cells had almost the same short-circuit current (= 40 rnA/cm2) as the
best modern cells, but an appreciably smaller open-circuit voltage (0.59 V
compared to 0.71 V). It is based on the more general version of Eq. (1.18) for
the reverse saturation current density J,, for uniform doping on both sides of
the junction,
where n, = (nopo)1/2,N A is the acceptor density in the pregion, N D is the

donor density in the n-region, D , and rn are respectively the diffusion constant
and lifetime of electrons in the p t y p e region, and D, and rPare respectively
the diffusion constant and iifetime of holes in the n-type region. Since the sat-
uration current density is essentially the thermally generated minority-carrier
flow in the dark, Eq. (2.1) indicates that J , is reduced with increasing values of
N A and N o . Equation (2.1), however, is no longer valid for degenerate doping
(n or p 2 l o ” cmP3) since then n: # n,po, the majority-carrier concentration
is not equal t o the impurity concentration, and Auger processes become im-
portant in determining the lifetime. Heavy doping of the n-type layer actually
leads to an increase in J,, a decrease in &-, a decrease in the fill factor, and
a decrease in the efficiency.
In general it is desired to have the doping in the thick p t y p e region to be

relatively low in order to yield longer diffusion lengths for the minority carrier
electrons. It is for the same reason that the thick region is chosen to be p t y p e
rather than n-type: because of the greater diffusion length of minority carrier
electrons in p t y p e compared to minority carrier holes in n-type.
The back contact to the p t y p e Si is produced by vacuum deposition of Al,
followed by a heat treatment that produces a p+-Si region by diffusion of the
A1 into the Si. By making a p + back layer, the contact resistivity is reduced,
and a “back surface field” (shown in Fig. 2.5 as BSF) can be produced to drive
carriers away from the back surface and hence t o reduce the effects of surface
recombination there. A doping technique that yields a p+-doping profile in
which it is possible to control both the doping concentration and the profile
thickness independently has been described (Loelgen et al., 1994) for boron
doping using co-alloying with aluminum.
The front-surface contact to the n-type side is in the form of a grid with
grid lines 0.03 to 0.3 cm apart, covering about 5 to 10% of the total area; the
grid is formed of multiple metal layers, such as Ti/Pd/Ag, to improve bonding
and inhibit undesirable electrochemical reactions. Finally, an anti-reflection
coating must be used, since the reflectivity of Si over the spectral range of
interest varies from 33 to 54%; a variety of materials have been used, including
Si02, Si3N4, and Ta203.
The Violet Cell

An early type of Si p-n junction, called the “violet” cell (Lindmayer and Allison
1973) had a very thin n-type layer like that shown in Fig. 2.5 to increase
spectral response of the cell in the blue and violet portion of the spectrum. The
form of the cell is shown in Fig. 2.4(c). Such cells typically had q5,, = 0.59 V,
J,, = 40 mA/cm2, f f = 0.78, J , = lo-’’ A/cm2, A = 1, and 7 = 13.5% for
AM0 radiation.
The C N R Cell
Another early type of Si p-n junction solar cell was the T o m s a t non-reflective’’
(CNR) cell (Haynos et al., 1974; Arndt, 1975; Rittner and Arndt, 1976), some-
times also called the “black cell”. It was characterized by a physically tex-
turized front surface designed to reduce reflection losses and to cause photo-
generation closer to the junction by allowing light to travel in paths that are
not normal to the junction interface. Such cells typically had q50c = 0.59 V,
J,, = 46 mA/cm2, f f = 0.77, J , = 6 x A/cm2, A = 1, = 15.5%
for AMO, and Q = 18% for AM1 radiation. General issues related to coupling
sunlight to solar cells in a useful way are discussed by Luque (1993).
Other Types of Early Solar Cells

Examples of other less-efficient types of solar cells made with single crystal
Si include Schottky-barrier or MIS junctions, and SnOz or I T 0 junctions.
Efficiencies of 8% for an Al-oxide-Si junction (Charlson and Lien, 1975) and
8.5% for a Cr-oxide-Si junction (Anderson et al., 1974, 1977) were reported.
Heterojunctions of n-SnOa/n-Si have also been investigated using deposition
of SnO;? onto Si substrates followed by a short heat treatment (Mizrah and
Adler, 1977; Thompson et al., 1977; Nash and Anderson, 1977). Efficiencies
as high as 10% for AM1 irradiation were reported, but the cells underwent
degradation presumably due to the growth of the insulating oxide layer between
the conducting SnO2 and the Si.
Passivation of Top Surface

A major improvement in output voltage was achieved by improved passivation
of the top surface of the cell, using thermal oxide to passivate non-contacted
areas and various techniques to reduce recombination at the interface with
the top metal contact. A cell known as the PESC cell (passivated emitter
solar cell) had a reduced area of contact at the top surface, and ultimately an
efficiency over 20% was achieved for the first time with high-quality float-zone
Si wafers relatively highly doped with B (Green et al., 1985).
The Back Point-Contact ( B P C ) Cell

A major advance in efficiency was achieved by careful attention to material
control and cell design (Swanson et al., 1984; Sinton et al., 1985; Sinton et al.,
1986a; Sinton and Swanson, 1987a,b,c; del Alamo and Swanson, 1987a,b; Ver-
linden et al., 1987, 1988) with oxide passivation of both front and rear surfaces
of the cell. The cell structure is given in Fig. 2.6. Cells are formed on high-
resistivity float-zone Si substrates giving a p-i-n structured solar cell. Light-
trapping at the front surface is achieved by pyramidally texturing the surface,
and a back-surface mirror causes reflection of most of the non-absorbed pho-
tons at angles that result in total internal reflection. This light-trapping is
essential because of the need to keep the cell thin to minimize recombination
and maximize collection of the photogenerated carriers. Shading or recombi-
nation associated with contacts on the front surface is avoided by the use of
I
hv
Fig. 2.6. A cross-section of a region in a Si back-point contact solar cell near one of the A1
bussbars. (Reprinted with permission from R. A. Sinton et al., I E E E Electron Device Lett.
EDL 7,567 (1986). Copyright 1986, IEEE, NY.)
alternate p t y p e and n-type small point contacts only on the back surface. The
small size of the contacts allows a considerable decrease in recombination, but
contact resistance must be minimized. Careful attention is paid t o minimizing
the surface recombination velocity over the entire surface of the cell, and to
maintaining maximum bulk carrier lifetimes since carriers photoexcited near
the top of the cell must diffuse t o the contacts a t the back.
These were the first cells to exceed 22% efficiency under normal terrestrial
illumination. The most efficient cell reported has a thickness of 120 pm, an
area of 0.15 cm2 with a metal-finger length of 3 mm, and an efficiency of 28%
at 15 W/cm2 of AM1.5 illumination (about 150 suns). Figure 2.7 shows how
the efficiency varies with the concentration of the illumination, and Fig. 2.8
shows the calculated deconvolution of the recombination current a t the maxi-
mum power point for the cell of Fig. 2.7 (Sinton et al., 1986b). Over this range
of concentration, the measured open-circuit voltage increases from 650 mV a t
1 sun to 840 mV at 600 suns. The importance of recombination in the periph-
eral region, which dominates a t low concentrations, decreases with increasing
concentration, as does the recombination a t surface and bulk defects in the il-
luminated regions of the cell. Recombination in the emitter (diffused) regions
30 I I ' ' ""'I ' ' ' 'i"r

- Cell 11-38
28 - 24*1 t
8 4 f++I
5 26-
f f
c
.-a
-
.?
c
w
24 -
-
I
$I :
22'L
20. a I I I L 1 1 1 1 1 I 1 ,,,,.I I , , I ,,.u

I 10 100 1000
ii-
!
?
)
z
00
Auger
j 60- perimeter
0
c emitter
.G
4-
40-
a surface
.-
t
I
0
V
U
1 10 100 1000
Concentration, s u n s
Fig. 2.8. Calculated deconvolution of the recombination current at the maximum power point
of the cell of Fig. 2.7 into its components as a function of the concentration value. (Reprinted
with permission from R. A. Sinton et al., Copyright 1986, Sandia Report SAND86-0058/1,
Albuquerque, New Mexico.)
of the cells becomes increasingly important as the concentration increases,

and passes through a maximum with increasing concentration. At the highest
concentration levels, bulk Auger recombination dominates.
Some caution needs to be exercised in recognizing the differences between

differential (measured from a small periodic light to produce the measure-
ment signal superimposed on a constant bias light to define the injection level)
and actual surface recombination velocities (Brendel, 1995; Brendel and Wolf,
1995). The actual surface recombination velocity must be obtained by inte-
grating measurements of the differential surface recombination velocity over
all injection levels, and may be as much as several times larger than the latter.
Using a solar cell design of this type optimized for the purpose, the Auger
recombination process was investigated in more detail (Sinton and Swanson,
1987) over the range of non-equilibrium carrier densities from 1016 to 2 x
. Auger coefficient was evaluated to be 1.66 x lop3' cm6/s,
~ m - ~The
a value some four times larger than that most commonly assumed. These
results suggested that the lifetimes in the very best quality doped material
may already be approaching this fundamental Auger recombination limit and
that a common mechanism exists for recombination in both doped and highly
injected materials.
The initial rear point contact cells proved t o be unstable due to optical
degradation of the silicon/oxide interface in an effect apparently similar to the
optical instability of amorphous silicon solar cells due to the photogeneration
of defects, described in Chapter 4. In the case of the BPC cell, diffusion of
the exposed surface with P and deposition of an ultraviolet-absorbing material
such as Ti02 on the top surface appears t o have removed the problems of
instability (Verlinden et al., 1993).
A simplified BPC cell for use without concentration has been described,
which can be fabricated by a less complex process yielding a cell with an
efficiency of 21.9% at one sun (Sinton and Swanson, 1990). Developments with
the BPC cells are summarized in several more recent publications (Verlinden
et al., 1994a,b; Verlinden et al., 1995; Sinton et al., 1995).
The Passivated Emitter, Rear Locally-Diffused ( P E R L ) Cell

A record high efficiency for terrestrial illumination of greater than 23% has
been achieved in a cell that combines the best features of the PESC and BPC
cells, shown in Fig. 2.9 (Green, 1991). Inverted pyramids covered with a n anti-
reflection coating along the top surface increase the fraction of the incident
light effectively used in carrier generation in the cell. Weakly absorbed light
that passes through the cell is reflected by the rear oxide layer covered by
an aluminum layer. These two optical features of the cell increase the path
length of weakly absorbed light within the cell, giving an effective absorption
finger
\
"iyerted" pyramids
rear contact oxide

Fig. 2.9. Schematic of a passivated emitter, rear locally-diffused cell (PERL cell) which
has shown an efficiency for terrestrial illumination of 23% (Reprinted with permission from
M. A. Green, Silicon Solar Cells: Advanced Principles &' Practice, Centre for Photovoltaic
Devices and Systems, Univ. of New South Wales, Sydney, 1995.)
thickness about 30 times that of the physical thickness of the cell. Typical
output values for PERL cells are J,, = 41 mA/cm2, &c = 710 mV, ff = 0.83
and 77 = 24%. An efficiency greater than 45% has been measured with this
structure for 1.02 pm monochromatic light (Green et al., 1992) and of 46.3%
for 1.04 pm wavelength light (Zhao et al., 1995).
As far as recombination losses in these cells are concerned, it is believed
that bulk recombination can be made negligible using present designs with
appropriate processing conditions (Green, 1993a). Rear surface recombination
in non-contacted areas is not important at open circuit (the effective recom-
bination velocity decreases from large values of lo4 cm/s t o low values below
30 cm/s as the voltage increases from short-circuit to open-circuit values), but
is important at the maximum power point voltage, resulting in a reduction in
fill factor. At the open-circuit voltage, recombination in the top diffused layer
and its contact region dominates the behavior. A detailed investigation of the
limiting loss mechanisms in PERL cells has been made by Aberle et al. (1995).
High Eficiency Solar Cells f r o m FZ, CZ and mc-Silicon:

A Processing Summary
Developments in the production of high-efficiency solar cells using silicon pre-
pared by different methods (FZ - float zone (21.1%), CZ - Czochralski
50 Photovoltaic M a t e r d s
22 Oxide elchinp
Fig. 2.10. Illustration of a processing scheme for a high-efficiency silicon solar cell with a
boron back surface field. (Reprinted with permission from J. Knobloch et a!., 23rd ZEEE
Photovoltaic Specialists Conference, p. 271 (1993). Copyright 1993, IEEE, NY.)
(19.3%),and mc - multicrystalline (16.2%)) provide specific examples of the

typical processing steps in modern silicon solar cell development (Knobloch
et al., 1993). These LBSF (local back surface field) cells (Knobloch et al.,
1989) are similar t o the PERL cell described above. Subsequent work with
an optimized emitter, based on an understanding of the heavy-doping effects
described above, raised the efficiency of CZ-silicon cells to 21.3% (Knobloch

et al., 1995), and of FZ-silicon cells to 22.3% (Sterk et al., 1994; Glunz et al.,
1995). A large-area PERL silicon cell module with area of 743 cm2 has also
been reported with a n efficiency of over 20% (Zhao et al., 1993).
Figure 2.10 summarizes the processing procedure in cleanroom conditions
with a boron-doped BSF on FZ silicon. (1)-(6). Local boron diffusion. (7)-
(12). Surface texturing. (13)-(24). n++ diffusion with phosphorus from
POC13, followed by n+ diffusion with phosphorus. (25) SiOz passivation of
front and back surfaces, the front passivation layer aIso acting as an anti-
reflection coating. (26)-(30). Open the oxide at rear side at the points with
the local boron BSF, evaporate A1 on the whole rear side. (30)-(35). Open
the windows on the front side for the metal grid, evaporate Ti, Pd, and Ag,
lift off the excess metal in acetone, and electroplate silver on the front surface.
Anneal the cells a t 400-450°C for 20-30 minutes in forming gas consisting of
5% hydrogen in nitrogen. The current-voltage characteristics for the best cells
of each type are shown in Fig. 2.11. Boron-diffused BSFs proved superior t o
aluminum diffused BSFs for both FZ- and CZ-crystals. The specific efficiency
of the mc-silicon cells depended, not surprisingly, on the defect structure of
the silicon, being highest for the low defect structures, which behaved more
like the single crystal cells.
c
5 *
L
L
3
0
0
0.0 0.1 02 0.3 0.4 05 0.6 0.7
VoItoge p]
Fig. 2.11. Current-voltage characteristics for the best solar cells from FZ-, CZ- and multicrys-
talline silicon prepared by the processing schedule of Fig. 2.10. (Reprinted with permission
from J. Knobloch et al., 23rd I E E E Photovoltaic Specialists Conference, p. 271 (1993).
Copyright 1993, IEEE, NY.)
A simplified processing method for high-efficiency silicon cells involving an

emitter diffusion process with a near-ideal doping profile and a passivating ox-
ide in a single furnace treatment is described by Basore et al. (1994). Limiting
the processing to a single high-temperature treatment preserves the bulk life-
time, important particularly in lower-cost material with a high concentration
of oxygen or carbon. FZ efficiencies over 19%, and CZ efficiencies over 18%
are routinely obtained.
350
EJ)
C
3 250
c
.g 200
zb' 150
s
'
'jo 100
aJ
50
o ~ " " ' " " " " ' ' ' ' " '
0 200 400 600 800 1000
Dislocation Density (#/cmZ)
Fig. 2.12. Dependence of effective diffusion length on the dislocation density in CZ silicon
solar cells. (Reprinted with permission from K. L. Pads et al., 23rd IEEE Photovoltaic
Specialists Conference, p. 209 (1993). Copyright 1993, IEEE, NY.)
Recent developments in all areas of CZ technology have been described with

the goal of achieving module costs under $2/Wp (Mitchell, 1994; Mitchell et al.,
1994).
Rapid thermal processing (RTP), using incoherent light sources with a wide
spectrum, has been used in the fabrication of large area n+pp+ silicon solar
cells with an efficiency of 15% on 10 cm2 CZ silicon wafers (Sivoththaman
et al., 1995). Two short (50 s) RTP steps were used for emitter formation,
BSF formation, and surface oxidation. Initial work was also reported on the
use of spectral selection of the light in rapid thermal processing (Noel et al.,
1995). By selecting parts of the spectrum of incoherent RTP light, it was
possible to "tailor" the profiles of phosphorus doped emitters, thus allowing
selectively doped areas without masking or etching. Several other discussions
have been given of the potential application of RTP to multicrystalline silicon

solar cells (Hartiti et al., 1993, 1994; Schindler et al., 1993; Ventura et al.,
1994; Hahne et al., 1994).
Slip dislocations are known to occur in CZ material, and the importance
of these dislocations for solar cell applications has been investigated by Pauls
et al. (1993). Dislocations are in some ways similar to grain boundaries,
discussed in Sec. 2.7, but the difference is that dislocations consist of a line of
charged defects whereas grain boundaries consist of a sheet of charged defects.
Effective minority carrier diffusion lengt,hs were calculat,ed from the measured
quantum efficiency of solar cells using standard spectral response equations
for specimens with different dislocation densities, with the results shown in
Fig. 2.12. For low dislocation densities, the diffusion length is about 250 t o
300 pm, but it decreases to less than 100 pm if the dislocation density increases
to 800 cm-’. In spite of this the cell efficiency decreases only from 15-16% for
low dislocation densities to about 14% for a dislocation density of 800 cm-2,
but then decreases rapidly for higher dislocation densities due to the reduced
carrier collection from the bulk.
2.5. Increasing the Efficiency of Silicon Cells

General considerations leading to possibilities of increasing the efficiency of
silicon solar cells have been summarized by Green (1993a).
Increasing the Current

An increase in the solar cell current can be obtained by having effective absorp-
tion of a greater portion of the solar spectrum. One way to achieve this is by
having regions of the cell consist of material with a lower band gap than silicon.
Such effective band-gap lowering can in principle be achieved by selective dop-
ing, alloying, and use of electric fields to reduce the band gap (Franz-Keldysh
effect). Of these conceivable approaches, only alloying appears to be really
promising; alloying with germanium is the most likely approach, and initial
research is being undertaken (Ruiz et al., 1994; Wollweber et al., 1994; Borne
et al., 1994; Losada et al., 1995).
A mechanism for an increased quantum effciency is the utilization of carrier
multiplication by hot carriers (Auger generation) in the wavelength regime of
visible light (Werner et al., 1994a,b, 1995a). Sil-,Ge, alloys with z = 0.6-0.7
have been suggested as possible solar cell materials in which carrier multi-
plication by Auger generation would lead to a n increased current (Kolodinski
et al., 1995), and experimental verification of this possibility has been achieved
(Werner et al., 199513). For a terrestrial cell, the predicted theoretical maxi-
mum efficiency including this process is 44.2%.
Another way to increase the solar cell current is to make use of multiple-step
absorption through defect levels in the forbidden gap in silicon. The danger
here, of course, is that an increase in defect density corresponds to an increase
in recombination loss. It has been concluded, however, that impurity levels
lying closer to the band edge than to midgap can in principle improve the
current output without major loss in cell voltage.
These various methods of increasing the current in a Si cell by the effective
use of subgap absorption emphasize the need for an accurate knowledge of the
absorption of intrinsic silicon over the whole solar spectral range. Keevers and
Green (1995) used sensitive subgap photocurrent measurements on high effi-
ciency PERL silicon solar cells to determine the absorption coefficient between
1.19 and 1.45 pm. These measurements have been augmented by previous data
for shorter wavelength light and the absorption over the whole range from 0.25
to 1.45 pm is listed by Green (1995a). A plot of the spectral dependence of
the absorption coefficient corresponding to these data is given in Fig. 2.13.
They cover 14 orders of magnitude of the absorption coefficient, and the long
wavelength fine structure giving rise to inflection points at 1.18 pm, 1.25 pm,
and 1.34 pm corresponds to the l-phonon edge, the 2-phonon edge, and the
3-phonon edge respectively.
Increasing the Voltage

The magnitude of the open-circuit voltage in high-efficiency PERL cells is
limited by recombination along the top surfaces of the cell. Improvements in
design and processing should allow the voltage to reach limits determined by
Auger recombination in the bulk of the cell (Green, 1984). It is predicted
that the highest voltages will be obtained in lightly doped material with the
maximum open-circuit voltage being given by:
4oc = (2/3) ( k T / q ) ln[JL/(qng(Cn + C,) W)l (2.2)

where Jr, is the light-generated current density at & c , ni is the intrinsic carrier
concentration, W is the cell thickness, and C, and C, are the electron and
hole Auger recombination coefficients in silicon (Green, 1987). Using current
values of ni = 1 x lo1' (Sproul and Green, 1991) and C, = C, =
1.66 x lop3' cm6 s-l at 300 K, gives a value for the maximum &c of 748 mV
for a 280 pm thick cell. Experimental values on actual cells are approaching
this value.
Absorption Constant (l/cm)
2.6. Novel Structures

Several different novel structures have been proposed to increase the efficiency
and utility of single-crystal silicon solar cells.
Vertical Multifunction Cells ( V M J )

This term has been used to describe two different types of cells: (a) a stacked
VMJ: an edge-illuminated stack of discrete p n junction cells so that the open-
circuit voltages add, used to increase the open-circuit voltage for concentrating
systems (Goradia et al., 1976), and (b) a convoluted VMJ: a single p-n junction
cell with a convoluted junction plane, designed to increase radiation tolerance
and for use in concentrating systems (Frank and Goodrich, 1980).
Tandem Junction Cells

Tandem cell structures in general consist of two of more cells each involving
material with a different band gap, so that the light which passes through the
upper cell of the tandem structure with a larger band-gap material, can be more
efficiently absorbed in the lower cell with a smaller band-gap material. Silicon
has an appropriate band gap to be used as the lower cell in such a tandem
structure. The problem, however, is that there are not many materials with
a suitable lattice constant and band gap t o serve as an epitaxially grown top
cell on the silicon (Corkish, 1991), so that a buffer layer of higher band gap
than silicon is needed to take up the lattice mismatch and also possibly to
provide electrical connection between the top cell and the lower-lying silicon
cell (Yamaguchi, 1992).
Silicon Spheres
Solar cells have been fabricated using inexpensive material as feed stock, and
then growing single crystal 1-mm-diameter spheres of silicon by melting silicon
particles (Levine et al. 1991; Levine, 1992; Ahrenkiel et al., 1996). The process
in which small-diameter spheres are grown provides a purification step by di-
rectional solidification, allowing for the use of highly impure starting material.
The starting material is melted and then single crystal spheres are formed by
the surface tension from small droplets of melted silicon. Impurities segregate
to the surface of the spheres, which is removed in a repeated process to produce
sufficient purification for solar cell use. The spheres are commonly B-doped
p t y p e , and a p n junction is formed on the entire outer surface by P diffusion.
The spheres are pressed into small orifices in an A1 foil that makes contact
with the n-type surface, the top of the spheres are etched back t o reveal the
D-type interior doping, and a contact is made to the inner p t y p e material
with a second foil, the two foils being electrically insulated from each other by
deposition of a polymer. Because of their geometry the cells are particularly
2fficient a t collecting diffuse light. A power module consisting of forty 100 cm2
:ells has demonstrated an efficiency of 10.3%.
Recombination lifetime studies on these silicon spheres has been carried
mt using radio-frequency photoconductivity decay (Ahrenkiel et al. , 1996),
-omparing cells made from metallurgical grade silicon with those made from
4ectronic grade silicon. After two melting cycles, the lifetimes of cells made
From electronic grade material are a n order of magnitude larger than those
made from metallurgical grade material.
Superlattices
The possible application of superlattice design to silicon solar cell developments
should be included in this discussion. To date most attention has been given
to silicon/germanium superlattices, in which the presence of strain introduces
new effects of possible ultimate interest (Barnham et al., 1990, 1991).
2.7. Thin Multicrystalline Silicon Solar Cells

Detailed discussions of multicrystalline silicon thin films for solar cells are
given in (Fahrenbruch and Bube, 1983; Van Overstraeten and Mertens, 1986;
Werner et al., 1994c; Green, 199313, 1995a; Bergmann et al., 1997). Werner
et al. ( 1 9 9 4 ~provide
) a comprehensive review of the literature.
General
The use of thin multicrystalline silicon cells offers five major advantages: (1)
less material is needed without loss of current provided that light-trapping
is adequate; (2) somewhat lower quality material can be used since smaller
diffusion lengths can be tolerated in thin cells; (3) theoretically thin cells can
produce higher open circuit voltages and hence efficiencies than thick cells with
the same bulk diffusion length; (4) thin cells are more radiation-resistant; and
( 5 ) a major advantage in economy of growth.
The use of multicrystalline materials in solar cells, however, introduces
several new challenges. Major considerations concern the control of nucle-
ation and growth of crystalline Si on foreign substrates at low temperatures,
the need for a high-quality light-trapping scheme since the thickness of the
material available for a one-pass absorption of the light is reduced (Redfield,

1974), more effective surface passivation as the film thickness decreases and the
effective ratio of surface to bulk increases, and passivation of grain boundaries
to eliminate their deleterious effects.
Werner et al. (1994~)summarize the following physical characteristics re-
quired for an effective thin film cell: (1) cell thickness W between 10 pm and
100 pm, (2) effective light-trapping with transparent material in direct contact
with both sides of the Si absorber, ( 3 ) bulk diffusion length L greater than the
cell thickness, (4) electrically inactive grain boundaries, or grain sizes much
greater than the diffusion length, and (5) back surface recombination velocity
less than or equal to the diffusion velocity v d = D / L , where D is the diffusion
constant.
Grain Boundary Effects

In addition to an increased density of defects in general (dislocations, stacking
faults, and twinning planes) compared to single-crystal silicon because of re-
duced control of the crystallization process, a multicrystalline material is made
up of grains with different crystalline orientations. The grain boundaries be-
tween these grains are characterized by interface states leading to a potential
barrier between the grains, which have some similarity t o the type of structure
expected near a surface, i.e. in some ways a grain boundary can be thought of
as a kind of “internal surface”.
Figure 2.14 shows a simplified energy band diagram of a n intergrain barrier
in an n-type polycrystalline material. It is likely that grain boundary states
are distributed across the gap with a high density near the band edges and
probably a local maximum about one-third of the way across the gap (Jackson
et al., 1983), similar to the density of states often associated with amorphous
silicon (see Chapter 3 ) . The grain boundary interface states below the Fermi
level are negatively charged, and the grain boundary interface is surrounded
on both sides by semiconductor depletion regions with a positive charge. It is
evident from the figure that the minority carrier holes in this case experience
a local field a t the grain boundary which enhances their probability of being
captured at a grain boundary interface state, thus decreasing the minority
carrier lifetime. It is also evident that majority carrier electrons experience a
potential barrier at the grain boundary which decreases their effective mobility
and increases the resistivity of the film for majority carriers. The effect of
photoexcitation is generally to increase the density of majority carriers and to
Fig. 2.14. Energy band diagram for a grain boundary in an n-type polycrystalline material.
decrease the height of the grain boundary potential barriers, thus increasing
the majority carrier mobility, and the film conductivity (Bube, 1992).
A general schematic diagram for a thin film polycrystalline solar cell is given
in Fig. 2.15, illustrating the difference between horizontal grain boundaries ly-
ing within n- or p t y p e material, and vertical grain boundaries crossing the
interfaces between n- and p t y p e regions. Horizontal grain boundaries may re-
duce the short-circuit current because of a decrease in minority carrier lifetime
through an increase in the density of sites for recombination, and vertical grain
boundaries may reduce both the short-circuit current and the open-circuit volt-
age if they intersect the junction boundary and provide effective shorting paths
that increase the reverse saturation current. In addition, grain boundaries may
also increase the diffusion of impurities by rapid diffusion along grain bound-
aries, and provide favorable sites for impurity segregation due to a kind of
gettering effect.
It is believed that grain boundaries in Si are symmetrically depleted with
about the same activity in n-type and p t y p e material , and that the elec-
tronic properties of these grain boundaries are not dominated by such intrinsic
properties as dangling bonds, but by extrinsic (impurity-related) properties
(Werner et al., 1 9 9 4 ~ ) .The presence of oxygen and carbon, as well as many
transition metals within the boundary plane, strongly alters the properties of
Si grain boundaries.
The formation of photoinduced metastable defects associated with dan-
gling bonds has been reported for hydrogenated polycrystalline silicon (Nickel
et al., 1993; Redfield and Bube, 1996) with many similarities to the effects ob-
served in amorphous silicon as described in Chapter 3. Electron spin resonance
depletio
region
Fig. 2.15. Thin film polycrystalline silicon solar cell showing grain boundaries: (a) horizontal
boundary in bulk region; (b) horizontal boundary in depletion region; (c) vertical grain
boundary. (Reprinted with permission from M. A. Green, Silicon Solar Cells: Advanced
Principles €9 Practice, Centre for Photovoltaic Devices and Systems, Univ. of New South
Wales, Sydney, 1995.)
identifies the defects as dangling bonds (Johnson et al., 1982), hydrogenation

decreases the density of dangling bonds (Kamina and Marcoux, 1980), and
hydrogen decreases the concentration of weak Si-Si bonds at or near the grain
boundaries (Jackson et al., 1983). There are, however, definite differences be-
tween polycrystalline Si and amorphous silicon (a-Si:H): (a) In polycrystalIine
silicon, the defects are essentially confined t o the two-dimensional grain bound-
aries, (b) grain boundaries in polycrystalline Si show long-range order, whereas
a-Si:H displays only short-range order, (c) the total density of metastable de-
fects in polycrystalline silicon is generally smaller than in a-Si:H since the
defects are confined to the grain boundary regions, and (d) unlike the case
in a-Si:H, the density of photoinduced defects decreases with repeated illu-
mination and anne'al cycles, and is restored upon re-exposure to monatomic
hydrogen. Although the production of photoinduced defects in a-Si:H solar
cells is a principal mechanism for cell degradation (see Chapter 3), a similar
effect has not been reported for multicrystalline Si solar cells.
Cast Multicrystalline Wafers

One approach t o making thin-sheet silicon solar cells is a conventional casting
process (CC) Chat produces multicrystalline ingots that may then be sawed into
wafers (Hubbard and Cook, 1989; Watanabe et al., 1990). In a process known
as the “Heat Exchanger Method” (HEM), a heat exchanger is positioned at

one end of the reservoir of molten Si to establish a n almost one-dimensional
temperature gradient; the castings produced by HEM are of excellent quality
with grain sizes of several millimeters or more, and all grain boundaries are per-
pendicular to the plane of slices made from the casting (Khattak and Schmid,
1980). An example of a production process for low-cost multicrystalline sili-
con solar modules with 16% encapsulated efficiency is given by Verhoef et al.
(1994). Improvements in the homogeneity of multicrystalline silicon ingots
with columnar grain structure are described by Schaetzle et al. (1993). A con-
tinuous casting method (CCM) designed to produce low-cost silicon wafers,
known as the “Drip-controlled method”, has been developed (Goda et al.,
1994). A record high efficiency of 18.6% has been reported for mc-Si solar
cells fabricated by a process that involves impurity gettering and back surface
passivation of 0.65 ohm-cm mc-Si grown by HEM (Rohatgi et al., 1996).
A process called electro-magnetic casting (EMC) has been developed
(Kaneko et al., 1994; Kawamura et al., 1994) t o produce a potentially in-
expensive material characterized by a small grain size associated with a short
diffusion length, but containing less oxygen and other impurities because of
the absence of contact between the walls of the crucible and the molten silicon
during growth. Hydrogen passivation is reported t o be effective in improving
the quality of EMC material, and an efficiency of 16% is reported on 4 cm2
cells by combining surface oxide passivation, hydrogen passivation by remote
plasma from the front side and by rf plasma from the back side (Elgamel et al.,
1994a,b,c, 1995; Rosmeulen, 1994). It was found that more hydrogen could
be incorporated in the EMC multicrystalline silicon than in the CC material,
probably because of the larger oxygen content in the CC material (Ghannam
et al., 1994).
(‘Ribbod7 Technology
Various procedures belonging to variations on a “ribbon” technology in which
sheets/ribbons/foils of Si for solar cells are produced, have been developed
to allow lower cost of multicrystalline Si solar cells, while giving up some.of
the efficiency (Goetzberger and Rauber, 1988). They include (1) dendritic
web (WEB) with shaping by two dendrites (Hopkins et al., 1987), (2) edge-
defined film-fed growth (EFG) with shaping by a graphite die (Wald, 1987),
(3) melt-spinning (MS) with casting in a graphite die (Madea et al., 1987),
(4) ramp-assisted foil technique (RAFT) with foil growth on a reusable ramp
(Beck et al., 1987), (5) horizontal supported web (HSW) with wedge-shaped
growth initiated by a graphite net (Falckenberg et al., 1987), ( 6 ) silicon sheets

from powder (SSP) with zone melting of powder layers using optical heating
(Eyer et al., 1987), and (7) embedding a matrix of small, spherical solar cells
into perforated aluminum foil (Levine et al., 1991).
Only the WEB (efficiencies of about 17%) and EFG (efficiencies about
15%) techniques have reached the stage of pilot plant activity. In the WEB
technique, two naturally arising parallel dendrites form the boundaries of a
web or ribbon pulled from a supercooled Si melt. The quality of the ribbon
is equal to good Czochralski single-crystal material. In the EFG technique a
carbon die with a slot-shaped aperture is immersed part way in a vessel of
molten Si. The liquid Si wets the die and flows through the slot t o feed the
solid zone above. The shape of the ribbon is controlled by the shape of the
top surface of the die, by surface tension, temperature gradients, and the pull
rate. Ribbons are flexible enough to be wound on large drums and ribbons
20 m long have been grown in a single run. No polishing is required. EFG
ribbon Si has rather high dislocation and twinning densities, which limit the
efficiencies achievable in solar cell applications.
Thin Film Cells on Silicon Substrates

One approach to thin film Si cells is to use Si itself as a substrate. There
have been two main ways that this has been attempted: by thinning a thicker
Si wafer (Uematsu et al., 1990; Nunoi et al., 1990; Somberg, 1990; Hezel and
Ziegler, 1993), or by epitaxial deposition of Si on a Si substrate using techniques
like liquid phase epitaxy (LPE) and chemical vapor deposition (CVD) (Wagner
et al., 1993; Rodot et al., 1987; Ciszek et al., 1993; Zheng et al., 1994; Fujimoto
et al., 1993; Oelting et al., 1993; Bergmann et al., 1994; Werner et al., 1994d).
Efficiencies of cells produced in this way range about 11% to 17%, with the
highest value of 17.3% achieved for a diffused p-n junction formed by CVD
deposition on a (100) p+-Si substrate (Werner et al., 1993, 1994d).
Thin film solar cells have also been fabricated with efficiencies as high as
9.3% by recrystallizing (using a large area heater, or by zone melting) 30-
50 pm thick Si layers on 2 mm thick SiOz intermediate layers, deposited on Si
substrates (Hebling et al., 1996).
Thin Film Cells on Foreign Substrates

The fabrication of both low-cost and efficient thin film cells has several fun-
damental requirements (Werner et al., 1 9 9 4 ~ ) (1)
: deposition of Si on foreign
substrates, (2) efficient light trapping, ( 3 ) passivation of grain boundaries and

surfaces, (4) gettering techniques, and (5) development of low-temperature
processing techniques suitable for the substrate used.
The substrates themselves should have a low manufacturing cost, chemical
and mechanical stability during Si deposition and processing, sufficient purity
to avoid contamination of the active Si film, a thermal expansion coefficient
close to that of Si, and should be optically transparent and electrically insu-
lating. Materials suitable for high-temperature processing (> 1000°C) include
graphite, quartz glass, most ceramics and oxidized Si (which could be consid-
ered as a “foreign” substrate if deposition takes place on the oxide).
Glass is a good candidate for a low-temperature substrate (< 6OOOC). A
procedure for low-temperature surface passivation suitable for use with silicon
on glass substrates has been reported (Langguth et al., 1995), involving grow-
ing a thermal pre-oxide by a short anneal at T < 680°C to obtain a low defect
density at the Si/SiO2 interface, and depositing a top-oxide by reactive evap-
oration of Si02 at room temperature to supply fixed oxide charge. The solid
phase crystallization of amorphous Si on glass substrates has been investigated
to grow large-grained polycrystalline Si (Bergmann et al., 1995).
A high-temperature-resistant glass substrate (stable up t o 1000°C) was
coated with a thin film of amorphous Si, which was then solid phase crystal-
lized during atmospheric pressure chemical vapor deposition of a several micron
thick light absorbing film (Bergmann et al., 1996, 1997). Thin crystalline sili-
con solar cells have been deposited by direct high-temperature (1000°C) CVD
from SiHC13 on temperature-resistant glass substrates (Brendel et al., 1997).
The measured diffusion length is only 0.6 pm in these cells, but theoretical
modeling indicates that a sufficiently thin (0.4 pm) film of this diffusion length
could yield 10% efficient cells, and a cell thickness of 1 pm could yield efficien-
cies of 15% for material with a diffusion length of 5 pm.
Examples of processes showing promise in the development of thin-film Si
solar cells involve the deposition of thin solar grade Si layers on a rigid ceramic
substrate, which has shown large area (78 cm2) efficiency of 8.5%, and small
area (1 cm2) efficiency of about 15% (Barnett et al., 1989, 1991, 1993), and
the recrystallization of Si thin films deposited on oxide layers on single-crystal
Si substrates by a special surface melting technique (Reis et al., 1988; Arimoto
et al., 1993; Ishihara et al., 1993). There are also several interesting attempts
to deposit Si on low temperature substrates, but further research is needed for
an adequate evaluation. In the effort to find a lightweight, low-cost substrate
for thin polycrystalline Si solar cells, a 13.4% efficient solar cell has been pro-
duced by a thin layer of polycrystalline Si grown directly on a filament-based
graphite fabric substrate (Rand et al., 1994). Multicrystalline Si layers have

also been grown on graphite substrates in an atmospheric pressure by rapid
thermal chemical vapor deposition (RTCVD) method using trichlorosilane and
the dopant trichloroborine diluted in hydrogen (Monna et al., 1996).
Passivation procedures
The grain boundary potential barriers in both n- and p t y p e silicon are re-
duced by the diffusion of monatomic hydrogen into the grain boundaries (Au-
couturier, 1991; Sopori et al., 1991; Seager et al., 1982; Rohatgi et al., 1993).
There is a decrease in the density of trapping sites for majority carriers, and a
decrease in the recombination velocity by a couple of orders of magnitude for
minority carriers. Still the fundamental microscopic mechanism is not com-
pletely understood. The extent of the passivation depends on the specific ori-
gin of the boundaries, and results not only from removing dangling bonds, but
also electronic defects related to impurity segregation. Both grain boundaries
and dislocations in LPE-grown Si appear to have a much lower recombination
velocity than those in the substrate, suggesting intrinsic gettering and bond
reconstruction during the near-equilibrium LPE growth of the film.
Another possibility for effective passivation of thin-film solar cells is the
plasma enhanced chemical vapor deposition (PECVD) of silicon nitride (Mich-
iels et al., 1990; Szlufcik et al., 1994; Schetter et al., 1995). It can serve as a n
antireflection coating and passivating layer, and can be deposited in existing
commercial systems. Strong enhancement of the bulk and surface passivation
from a plasma nitride layer has been reported during a fast firing for screen
printing metallization.
Gettering techniques
Effective gettering for a thin-film solar cell where the entire volume is electron-
ically active, requires the movement of impurities to the surface. Techniques
with P and A1 gettering have been reviewed (Verhoef et al., 1990; Gee, 1991;
Rohatgi et al., 1993; Porre et al., 1993; Perichaud et al., 1993), as has getter-
ing with P and C1 (Jastrzebski 1995). Verhoef et al. (1990) reported diffusion
experiments indicating that impurities such as copper, gold and nickel are
effectively gettered at the aluminum-doped layer. Gettering in single- and
multicrystalline silicon has been compared, using P, Al, and C1 gettering, as
well as back-side hydrogen gettering, and ultrasound treatments (Sopori et al.,
1996).
Multilayer Thin Film Silicon Solar Cells

Another approach to the development of high efficiency silicon solar cells on
lower quality material is that associated with multilayer thin film cells (Wen-
ham et al., 1994; Sproul et al., 1994; Green and Wenham, 1994; Green 1995c)
made with multicrystalline silicon. The process consists of depositing a di-
electric layer such as silicon oxynitride/nitride on a cleaned glass superstrate,
followed by the deposition of five to ten layers of silicon. Alternate layers are
doped with a different dopant impurity to give p- or n-type properties. A
process like chemical vapor deposition can be used for the deposition of this
multilayer stack. Finally, a silicon oxynitride/nitride layer is deposited on the
top surface as a capping layer, producing a total thickness between 10 and
20 pm. Then, using the technique for making buried contact cells, a laser is
used to form one set of grooves of one type of polarity connecting all the n-type
layers within the stack in parallel, and a second set of grooves which join all
the p t y p e layers, followed by metallization of the grooved areas.
The structure can be thought of as a number of very thin cells all con-
nected in parallel, with the thickness of each layer chosen to be smaller than
the carrier diffusion length within that layer, thus insuring that most of the
carriers photogenerated in the stack are collected. The theoretically expected
efficiency increases from less than 8% for a single junction to over 15% for six or
more junctions, assuming that the primary loss mechanism can be attributed
to uniformly distributed defects. The stacked cells should also be much less
sensitive to the effects of grain boundaries.
Contactless Techniques for Characterization

In evaluating the properties of materials for multicrystalline silicon solar cells,
it is advantageous to be able to make a spatially resolved measurement of the
lifetime or diffusion length of carriers in the material without contacts to the
material.
Modulated free-carrier absorption (MFCA)

A technique known as “modulated free-carrier absorption (MFCA)” has been
developed (Glunz et al., 1994c, 1995) which is able to probe the excess minority
carrier distribution over a wide area. In this method, photogenerated free
carriers are optically monitored by the absorption of infrared light. A phase
shift between the generation light and the IR transmission occurs due to the
lifetime of the carriers. An effective lifetime can be determined from this phase
shift, and in order to reach a high spatial resolution, the infrared laser beam
is focused on the sample (light-spot diameter < 100 pm).
Light-beam induced luminescence (LBIL)

A standard technique for the measurement of the diffusion length L of carriers
in a solar cell is electron-beam or light-beam induced conductivity (EBIC or
LBIC) (e.g. see Fahrenbruch and Bube, 1983). The current is measured as a
small region of the material is excited by an electron beam or a light beam
at a varying distance z from the junction. For moderate to large values of
x / L , the short-circuit current of the cell is given by I,, = Aexp(-z/L). It has
been shown that a contactless method for obtaining similar information can
be obtained from light-beam or electron-beam induced luminescence in silicon
(Daub et al., 1994), which is applicable both t o unprocessed wafers and t o
completed solar cells.
2.8. Microcrystalline Silicon
Applications of p t y p e pc-Si:H and pc-Si:C:H in a-Si:H solar cells are described

further in Secs. 3.9 and 3.10. A number of results have been reported for solar
cells involving pc-Si:H deposited by the Very High Frequency Glow Discharge
(VHF) method (Finger et al., 1993) which is also described in connection with
a-Si:H deposition in Sec. 3.6. Structural investigations of pc-Si:H indicate
that it is a composite material made up of crystalline grains, grain boundaries
and an amorphous phase. The VHF technique involves deposition in a glow
discharge at a n excitation frequency of 70 MHz from silane (1.5%) diluted in
hydrogen, with phosphine and diborane as dopant gases. Initial investigation
indicated that electrical transport in pc-Si:H cannot be described by means
of a single activation energy, but instead evidence exists for a distribution of
activation energies probably correlated with a distribution of grain sizes and
grain boundary defect densities.
A number of reports exist on the use of these VHF-deposited pc-Si:H layers
in p i - n solar cells (Flueckiger et al., 1993, 1995a, 199513; Meier et al., 1994a,
199413; Meier et al., 1996). The as-deposited pc-Si:H was slightly n-type, and
compensation was obtained by boron-doping. Entirely pc-Si:H p i - n type solar
cells were fabricated incorporating the compensated layer, with first results
yielding an efficiency of 3.8% and apparently better stability than standard
a-Si:H cells. The pc-Si:H cells showed larger infrared response beyond 750 nm
compared to a-Si:H cells because of a smaller effective band gap of about 1 eV.
Subsequent work raised the efficiency t o 4.6% and indicated that exposure t o
solar illumination did not degrade the totally pc-Si:H cells. An a-Si:H/pc-
Si:H stacked cell showed an efficiency of 9.1%, which did not degrade after
280 hours of intensive illumination with a sodium lamp with brightness of
about six suns. It is suggested that the electronic behavior of the pc-Si:H is
controlled by the crystalline phase in these materials. A beginning has also
been made on understanding the transport properties of compensated pc-Si:H
(Wyrsch et al., 1996) and the enhanced optical absorption of pc-Si:H (Beck
et al., 1996). The potential utility of pc-Si(l--s)Cz interface layers in a-Si:H
and mc-Si solar cells has also been investigated (Ma et al., 199413).
Microcrystalline-crystalline Si heterojunction solar cells were made using
a thin p + pc-Si:H window layer on top of 1 ohm-cm n-type single-crystal Si
(van Cleef et al., 1996). These cells had the following structure: Ag/ITO/p+
pc-Si:H/a-Si:H/n-Si/Al. A buffer layer consisting of intrinsic a-Si:H deposited
at low temperature was found to be essential in achieving high open-circuit
voltage and efficiency (12.2%).
CHAPTER 3
AMORPHOUS SILICON
3.1. Overview
Amorphous silicon is a thin-film material without long range atomic order that
can be deposited by a variety of techniques suitable for large area production.
In this form, however, amorphous silicon has a high density (of the order of
1019 cmP3) of coordination defects (“dangling bonds”) corresponding to de-
partures from the local tetrahedral coordination between four silicon atoms
(see Sec. 3.2). They act as recombination centers t o greatly reduce the carrier
lifetime and the carrier diffusion and drift lengths, and t o pin the Fermi energy
in such a way that the material cannot be effectively doped n- or p t y p e and
is not electronically useful. It was discovered, however, that the incorpora-
tion of about 10% hydrogen (from glow-discharge decomposition of silane gas)
during the deposition process greatly reduces the density of these defects to
about 10l6 cm-3 (Chittick et al., 1969), and this hydrogenated material can
then be doped n- or p t y p e to make useful semiconductor devices (Spear and
LeComber, 1976). A promising new thin-film silicon alloy, a-Si:H, had been
discovered.
Perhaps of greatest significance for photovoltaic applications, the hydro-
genated amorphous silicon alloy (a-Si:H) also has a higher-energy absorption
edge and a larger optical absorption constant for solar radiation than crys-
talline silicon. a-Si:H has a well-defined optical threshold at about 1.75 eV,
considerably larger and sharper than the indirect band gap of 1.1 eV of crys-
talline Si, as shown in Fig. 3.1, and only 1 to 2 pm thickness of a-Si:H is
required to absorb virtually all of the light above the absorption edge.
In the 20 years since this initial work, a voluminous literature has grown
up related to amorphous silicon. As examples we cite a general discussion of
amorphous silicon in a four-volume series edited by Pankove (1984), a two-
volume set edited by Fritzsche (1989), a book by Street (1991), and a two-
volume series edited by Neber-Aeschbacher (1995) containing thirty-six review
papers and sixteen original papers on many aspects of hydrogenated amorphous
silicon and its alloys. A portion of a book by Redfield and Bube (1996) is
68
Amorphous Silicon 69
Fig. 3.1. A comparison between the optical absorption coefficient for single crystal Si and a-
Si:H a s a function of wavelength. Long-wavelength d a t a are from Loveland et al. (1973/74).
(Reprinted with permission from D. E. Carlson and C. R. Wronski, A p p l . Phys. Lett. 28,
671 (1976). Copyright 1976, American Institute of Physics.)
concerned particularly with the properties of the defects and their induction
by photoexcitation.
It appears, therefore, that a-Si:H should be a n excellent choice for thin-film
solar cells: It is related to the general silicon technology and it can be relatively
inexpensively deposited in thin film form with high uniformity over large areas
on inexpensive substrates (e.g. glass) at low temperatures. Problems are asso-
ciated with the high density of defects still present even in the hydrogenated
material, and with the observation that the density of these defects increases
upon a variety of treatments of the material (see Sec. 3.3), particularly t o
exposure to high-intensity light (optical degradation). In spite of these insta-
bilities, a-Si:H has often been considered the front-runner in competition with
polycrystalline materials (see Chapters 5 and 6 ) for thin-film solar cells.
UNDOPED
a-Si
- hu
-Al
p/i/n JUNCTION
)TOJ
UNDOPED
0-Si
J UNDOPED -
o Si
d CONTACT PAD
hu
Pt SCHOTTKY
BARRIER
t t
n' a - S i ZroZ
Fig. 3.2. Three types of a-Si:H junctions: (top) a heterojunction between SnO2 and
a-Si:H, (center) a p z - n junction with p + - and n+-a-Si:H layers with undoped a-Si:H between
them, and (bottom) a Schottky barrier between Pt and n+-a-Si:H doped with P. (Reprinted
with permission from D. E. Carlson, IEEE Trans. Electron Devices ED-24, 449 (1977).
Copyright 1977, IEEE, NY.)
A variety of junction structures has been tested for solar cells using
a-Si:H, as indicated in Fig. 3.2. The most effective is generally agreed to be
a p a - n structure, consisting of an undoped insulating region between doped
p and n-type end regions, which makes it possible for the main absorber
portion of the cell to have the longer lifetimes of undoped a-Si:H, and for
the carrier collection process to be dominated by drift rather than diffusion.
Initial efficiencies as high as 12% had been obtained for single-junction cells
by the late '80's (Wronski, 1986; Hubbard, 1989; Hubbard and Cook, 1989).
The general improvements in a-Si:H solar cell efficiency are summarized in
Single junction cells ( I cm2)

Multigap cells ( I cm’)
Submodules (loo0cm2)
0
1975 1980 1985 1990
Year
Fig. 3.3. Improvement of a-Si:H based solar cells from 1975 to 1989. (Reprinted with per-
mission from E. S. Sabisky and J. L. Stone, 20th IEEE Photovoltaic Specialists Conference,
p. 39 (1988). Copyright 1988, IEEE, NY.)
Fig. 3.3 with data shown for small area single and stacked cells and for large
area modules (Sabisky and Stone, 1988). It is projected that the efficiency of
a multijunction cell may reach 20% by the year 2000 (Maruyama et al., 1995).
It is the effects of optical degradation that have limited the practical effi-
ciency of a-Si:H solar cells, and many attempts have been made to determine
the exact mechanisms involved in this process, to overcome defect formation
itself, or to redesign the solar cells so that the optical degradation effects are
minimized. These effects are discussed further in Secs. 3.3 and 3.8.
3.2. Electronic Structure and Dangling Bond Defects in a-Si:H

As an introduction to the use of a-Si:H in solar cells, we give in this section
a brief summary of some of the basic properties of the defects in a-Si:H. The
formation and properties of defect states in a-Si:H are discussed in fifteen

review papers in the volumes edited by Neber-Aeschbacher (1995).
Comparison with Crystalline Silicon

In spite of the absence of long range order in a-Si:H, many of the electronic
properties are similar to those of crystalline Si. As shown in Fig. 3.1, a sharp
optical absorption edge exists in a-Si:H, although it is displaced some 0.65 eV
toward higher energies compared to crystalline Si. Potential fluctuations in
the amorphous material, however, create electronic states which form a nearly
exponential distribution of band-tail states, which prevent a true density-of-
states band gap from existing in the amorphous material. In these tails carrier
mobility decreases to low values at low energies and a threshold known as the
102’ -l
0 0.5 1.o 1.5

Electron energy above valence band
eV
Fig. 3.4. Density of electron states in the band gap of a-Si:H, characterized by exponentially
varying valence and conduction band tails, and states associated with dangling bond defects
near the middle of the gap. (Reprinted with permission from D. E. Carlson and S. Wagner,
in Renewable Energy: Sources for Fuels and Electricity, eds. T . B. Johansson et al., p. 403,
Copyright 1993, Island Press, Washington, D.C.).
mobility edge exists in the energy spectrum of mobility. The gap that does
exist, between the mobility edge for electrons in the conduction band and the
edge for holes in the valence band, is a mobility gap, which is quantitatively
similar to the optical absorption threshold. Figure 3.4 gives a schematic plot
of the density of defect states in a-Si:H as a function of electron energy above
the valence band (Carlson and Wagner, 1993).
Diffraction patterns of quality a-Si:H show that nearly every Si atom is
bonded to four others in the same tetrahedral coordination as in crystalline
Si, with first and second nearest-neighbor distances similar to the values in
crystalline Si. The major difference is that in the amorphous material there is
an approximately 10" range of bond angles centered at the tetrahedral value
of approximately 109". The densities of amorphous and crystalline Si are
also approximately the same. The ideal structure for a n amorphous material
has been called a continuous r a n d o m network in which a complete amorphous
network of tetrahedrally bonded atoms can be formed, retaining the short-
range order except for small deviations in bond angles. The existence and
properties of hydrogen complexes in a-Si:H are discussed by Jackson and Zhang
(1990).
Native Defects
In this context a native defect in amorphous silicon can be seen as a departure
from the tetrahedral coordination of some particular Si atom t o four other Si
atoms: a broken Si bond, or a dangling bond. These defects are common to all
samples of amorphous silicon prepared around the world, and are identified by
a characteristic electron spin resonance (ESR) g = 2.0055 (Brodsky and Title,
1969; Taylor, 1984).
Actually ESR can detect only the paramagnetic species of dangling bond
with one unpaired electron; other possible states with zero or two unpaired
electrons are diamagnetic. The charge state of the defect in a particular mate-
rial depends on the location of the Fermi energy in that material; if the Fermi
energy is high in the gap then most defects will be in the diamagnetic D-
state occupied by two electrons, whereas if the Fermi energy lies close to the
valence edge, most defects will be in the diamagnetic D+ state, unoccupied
by electrons. When the Fermi energy lies close to the middle of the gap, as it
does in undoped, high quality a-Si:H, most defects will be in the paramagnetic
Do state with one unpaired electron. Both those defects that are present in
the dark after long times of thermal annealing, the so-called built-in defects,
and those that are induced by photoexcitation have the same ESR behavior.
74 Photovoltaic Materids
Another issue of considerable importance (see Sec. 3.4) is whether the de-
fects are intrinsic to the nature of the amorphous material, or whether they
are directly related to some extrinsic property such as a physical or chemical
abnormality (Stafford and Sabisky, 1987; Redfield and Bube, 1990; Redfield,
1991; Stafford, 1991).
Metastable defects in doped a-Si:H have been investigated by photomod-
ulation spectroscopy (Chen et al., 1992; Kocka et al., 1993). In addition to
information on the dangling bond defect (with state 0: in the dark, becoming
0%- or D: after capturing a photoexcited electron or hole, respectively) in
undoped material as summarized above, deep defects have been investigated
associated with phosphorus doping in a-Si:H:P (with state 0; in the dark,
becoming Dg after trapping a photogenerated hole), and with boron doping
in a-Si:H:B (with state DL in the dark, becoming Dk after trapping a photo-
generated electron). Exposure of a-Si:H:P to light produces both D p defects
and Di defects.
3.3. Modes of Defect Generation

In this section we summarize the different treatments of a-Si:H that lead t o an
increase in the density of metastable dangling bond defects. Several reviews
have been given (e.g. see Wagner and Smith, 1988; Neber-Aeschbacher, ed.,
1995; Redfield and Bube, 1996).
Doping with Standard Dopants (Beyer et al., 1977; Austin et al., 1979)
Doping a-Si:H with standard Si dopants such as phosphorus (n-type) or boron
(ptype) leads to an increase in the density of dangling bond defects if the
dopants are uncompensated, but actually to a decrease in defect density if
they are compensated (Amer and Jackson, 1984).
Quenching f r o m Elevated Temperatures

If a sample of a-Si:H is heated to a n elevated temperature (z220°C) and then
quenched, it is found that the density of dangling bonds is larger than the
initial room temperature value (Street et al., 1986). The density of dangling
bonds has been thermally increased] and the excess can be annealed away by
subsequent heating. A detailed investigation of thermal equilibrium processes
induced by thermal quenching effects in undoped a-Si:H has been reported
by Meaudre et al. (1991), who interpreted the results as indicating that the
equilibration temperature of the films is about 180-200°C.
Exposure t o High-Intensity Light (Staebler and Wronski, 1977)

When a-Si:H is exposed to high-intensity light such as sunlight, the density
of dangling bond defects increases until reaching a saturation value Nsatafter
long times of exposure. Both the dark conductivity and the photoconductivity
of the a-Si:H decrease; these effects can be annealed away at about 150°C. This
effect occurs for photon energies down to about 1 eV, even though the band gap
of a-Si:H is FZ 1.7 eV. Also, the density of light-induced defects in a material
increases with the density of defects induced in the material in the dark by
previous doping, as shown in Fig. 3.5 (Skumanich et al., 1985). Metastable
defects are formed with comparable efficiency a t all temperatures below 300 K
down to 4.2 K , showing that the creation mechanism is not thermally activated;
about 40% of the defects induced at 4.2 K anneal between 150 K and 300 K ,
indicating that low-T exposure creates defects that would not be stable for
high-T exposure (Stradins and Fritzsche, 1993).
0
10’
z
Q
/-
I, 0 Boron
I I
U-
/ 0 Phosphorus
A Compensaled-partial
A Compensated-full
($Typical Error Bar 1’
I I I
10’ 9
10’6 10’’ 1olB 1c
N (Defects/cm3)
Fig. 3.5. Correlation of the densities of light-induced defects A N with the density of defects
N present in the starting a-Si:H material for various doping conditions. (Reprinted with
permission from A. Skumanich et al., Phys. Rev. B 31, 2263 (1985). Copyright 1985,
American Institute of Physics, College Park, MD.)
In a number of different cases the description of the kinetics of defect for-

mation under illumination appears to fit very well with a so-called stretched-
exponential description, usually associated with dispersive phenomena having
a distribution of time constants (Redfield and Bube, 1996). It was shown
that the time-dependence of defect density during thermal annealing of these
light-induced defects can be described by a stretched exponential (Kakalios
et al., 1987), and subsequently similar results were demonstrated for the time-
dependence of defect formation under illumination based on a symmetrical rate
equation including both optical and thermal, formation and annealing terms
(Redfield, 1988, 1989). Without dispersion this rate equation was proposed to
be
d N / d t = C1R(NT - N ) - C2RN v ~ ( N T + -N ) - v ~ N (3.1)
where R is the total carrier capture (or recombination) rate, C1 and C2 are ef-
fectiveness coefficients for photoinduced generation and recovery of the meta-
stable condition, NT is the maximum density of possible defect centers and
v1 and v2 are analogous thermally-activated coefficients for thermally induced
generation and recovery, respectively. The quantity (NT - N ) is the density
of centers that are in their ground state and are thus available for defect for-
mation. Including dispersion, Eq. (3.1) becomes
d N / d t = (t/P)‘@-”[ C ~ R ( N-
T N ) - C2RN + v,(NT - N ) - v ~ N ] (3.2)
with solution
~ ( t= )Nsat - (Nsat - ~ o e )x p [ - ( t / ~ ) @ ]
(3.3)
Here p is the “stretch parameter” related to the breadth of the distribution
of contributing processes ( p < 1) and P is a scaling factor that preserves the
dimensions. No is the initial density of metastable defects, and T is an effective
time constant for the transient (Redfield, 1992). Nsat and T contain all four of
the coefficients in Eq. (3.1).
An example of the application of this formulation is provided by the mea-
surements of Park et al. (1989) using two different intensities of photoexcita-
tion on two different sampres, as analyzed by Bube et al. (1990), and shown
in Fig. 3.6(a). A convenient way to test the appropriateness of a stretched-
exponential description, and to obtain the value of the fitting parameter K
(writing the exponential in Eq. (3.3) as exp[-KtP]) is to rewrite Eq. (3.3) as
logf*(N) = logK + p1ogt (3.4)
where f * ( N ) = 1n[(Nsat - No)/(Nsat - N ) ] and is plotted in Fig. 3.6(b) for
the data of Fig. 3.6(a). For an actual stretched-exponential behavior, a plot of
lo'*] I
Fig. 3.6. (a) Comparison of experimental d a t a points from Park et al. (1989) for defect
density ( ~ m - ~in) a-Si:H with curves calculated from a stretched-exponential description
of optical degradation with a single fitting constant for all four curves ( 0 ) Sample A44, HI
(high-intensity Krf laser light), 343 K; (0)sample A62, HI, 343 K; (A) sample A44, LI
(lower-intensity tungsten-halogen light) 308 K; (0)sample A62, LI, 308 K. (b) T h e d a t a of
Park et al. (1989) given in (a), plotted using the form of Eq. (3.4) t o test t h e closeness of the
data to stretched exponentials, which produce straight lines in this kind of plot. (Reprinted
with permission from R. H. Bube et al., Appl. Phys. Lett., 5 7 , 79 (1990). Copyright 1990,
American Institute of Physics.)
logf*(N) versus logt yields a straight line with slope p and intercept log K .
Such stretched-exponential descriptions appear to be appropriate for a variety
of defect kinetics data obtained in recent years (Bube and Redfield, 1989).
An irreversible optical degradation of a-Si:H solar cells exposed to intense

illumination (50 suns) a t elevated temperatures (> 130°C) has recently been
reported (Carlson and Rajan, 1995, 1996). Unlike the optical degradation
induced at lower temperatures, this optical degradation is not reversed by
annealing and is not suppressed by a strong bias. Measurements indicate that
the effect is due to the diffusion of hydrogen at elevated temperatures both in
the dark and under intense illumination.
Exposure to Electron Beams (Street et al., 1979; Schade, 1984; Schneider

et al., 1987; Scholz and Schroeder, 1990, 1991; Grimbergen et al., 1993)
Metastable defects are formed in a-Si:H by high-energy (typically 20 keV)
electron beam irradiation similar to those caused by strong optical illumina-
tion. The major differences between the two defect production processes are
(a) the electron beam produces a higher density of defects, (b) the kinetics
for electron-beam defect generation follow a simple exponential rather than a
stretched exponential, although the kinetics for annealing of electron-beam-
induced defects does follow a stretched exponential, (c) the higher density of
defects induced by electron beam anneal more rapidly than defects induced
by light, (d) both electron-beam and light excitation cause a considerable de-
crease in the photoconductivity, but the dark conductivity, which decreases
for photoexcitation, actually increases for electron-beam excitation in undoped
material (Voget-Grote e t al., 1980).
Passage of Forward Currents i n Device Structures (Staebler e t al.,

1981; Crandall, 1987, 1991)
The observation that dangling-bond defects, the same as those induced by
light, are formed in the dark by passage of forward current in a p i - n device
led to the proposal that defects are not produced directly by the light, but
rather by the energy released when excess carriers recombine or are captured.
An investigation of light and current formation of defects in a-Si:H pi-,
n-i-n, and p-i-p structures indicated that defects are formed both by recom-
bination and by injection of holes, but not by injection of electrons (Ostendorf
et al., 1993).
Formation of a Space-Charge Region (Hepburn et al., 1986; van Berkel

and Powell, 1987; Deane and Powell, 1993)
When a voltage is applied to the gate electrode in a field-effect transistor
(FET), charges are trapped near the a-Si:H/dielectric interface. Analysis of the
somewhat complicated phenomena involved indicate that metastable defects

are formed in the a-Si:H itself by this field-induced effect without requiring
recombination to occur.
3.4. Models for Dangling Bond Defects

Because of their importance in determining the electronic properties and sta-
bility of a-Si:H, here we consider briefly a few representative models used to
describe the dangling-bond defects (Carlson, 1987; Redfield and Bube, 1996)
before proceeding to more general descriptions of solar cell development.
Configurational Coordinate Diagram

An appropriate description of the dependence of defect energies on local atomic
order or disorder calls for what has been named a “configurational coordinate”
representation (Baraff et al., 1980; Redfield and Bube, 1996). A simplified
version is given in Fig. 3.7, showing a plot of energy as a function of some
appropriately chosen configuration coordinate, e.g. the distance between two
CONFIGURATION COORDINATE
Fig. 3.7. Simplified configuration-coordinate diagram that is generally used for the dangling-
bond defect in undoped a-Si:H. The minimum on the left represents the ground state, and
that on the right represents the dangling-bond metastable state.
neighboring Si atoms. The left energy minimum in the figure corresponds

to the inactive ground state (often referred to as a L‘weakbond”) which sees
an energy barrier El for passing over into the metastable (“dangling bond”)
state, with energy barrier E2 for return to the ground state. The difference
AE = (El - Ez) can be inferred from high-temperature measurements of the
equilibrium density of defects and appears to have a value of about 0.2 eV.
Weak-Bond Breaking
Some variation of the concept of weak-bond breaking underlies most of the
models describing the origin of metastable dangling bond defects in a-Si:H. It
appears to be a natural inference from the fact that the normal Si-Si bond
strength is about 2.2 eV, but it is known that photoexcitation can produce
dangling bonds with photons with energy as low as 1 eV. The first, and perhaps
the simplest model, for the formation of dangling bonds is one in which weak
bonds are broken by the energy released by the recombination between free
electrons and holes formed by photoexcitation (Adler, 1984; Stutzmann et al.,
1985). This model predicted a variation of defect density as t1I3during optical
degradation, but later examination showed that the apparent agreement of
the data, more completely described by a stretched exponential as described
in Sec. 3.3, with such a t1/3 behavior was coincidental (Redfield, 1989; Bube
e t al., 1990; Bube and Redfield, 1992).
Distribution of Energies: Defect Pool Model

Because of the nature of the amorphous material, it is appropriate t o consider
a distribution of energy values, and this has been done in a number of models.
One of the most thoroughly investigated is the “defect pool model”, which
assumes a broad distribution of possible energies for the dangling bonds within
the energy gap (Smith and Wagner, 1987, 1989; Winer, 1990, 1991; Powell
et al., 1991, Branz et al., 1991, Hata and Wagner, 1992; Deane and Powell,
1993; Schumm, 1994; see also a review in Redfield and Bube, 1996). A weak-
bond state is associated with a state of the valence-band tail, and the valence-
band-tail width is taken t o be a measure of the structural disorder in the
material. An equilibrium description is used for defect reactions in terms
of a chemical-equilibrium equation relating the densities of weak bonds and
dangling bonds. Because of the broad distribution of possible defects, charged
as well as neutral defects can occur for any value of the Fermi energy. Hydrogen
atoms play a key role in bond switching. A representative equation is:
(Si-Si),b + Si-H + (Si-H)] + Do
4[Do (3.5)
Standard DDS
Defect Pool
. ~257meV
0.0 0.5 f .O 1.5

E-E, (eV)
Fig. 3.8. Calculated densities of states in the gap of a-Si:H using the defect-pool model
approach, showing the difference between the simple two-peaks (above), similar to that
obtained for a Gaussian distribution of energies for a single type of defect, obtained when
the correlation energy U is large, and the “defect-pool” result (below) when U is smaller.
(Reprinted with permission from G. Schumm, Phys. Rev. B 49, 2427 (1994). Copyright
1994, American Institute of Physics, College Park, MD.)
where (Si-Si),b is the initial, weak bond state; SikH is a separate complex of
a Si atom that is bonded to one H atom; and Do is a neutral dangling bond
state formed when the weak bond breaks.
A comparison is given in Fig. 3.8 between two energy distributions of the
density of dangling bonds calculated according to the same defect-pool formu-
lae, on top when u << U , and at the bottom when IJ E U , where IJ is the
width of a Gaussian distribution of energies, and U is the defect correlation
energy (the energy difference between when the defect is negatively charged
and when neutral, assumed the same for all defects t o be of the order of 0.2 to
0.3 eV). The results shown on top in Fig. 3.8 are quite similar t o those expected
when the dangling bond is described by a simple Gaussian shape in a discrete

energy-level model. The results shown on the bottom in Fig. 3.8 indicate the
consequences when the dangling bond is described by a typical defect-pool
model (Schumrn, 1994). The occurrence of various charge states a t different
places in the material is the consequence of a range of local environments.
Some apparent problems with the defect-pool model (DP) include (a) D P
predicts a greater density of charged defects than neutral defects even when
the Fermi level is at midgap, but measurements of ESR and capacitance are
essentially equal, indicating that most defects are neutral (Unold et al., 1994);
(b) D P calculations start with equilibrium relationships, and then apply these
procedures to steady-state, nonequilibrium conditions (Winer, 1990; Deane
and Powell, 1993); (c) Ganguly and Matsuda (1993) report that the bulk
defect density is determined by surface-controlled processes during material
deposition, and not by bulk equilibration; (d) relaxation of charged defect
states have been interpreted as ruling out a D P model (Cohen e t al., 1993).
Impurity-Induced Defects
It is known that uncompensated doping of a-Si:H increases the density of
metastable defects, as mentioned earlier. One of the early models for meta-
stable defects, proposed by Street (1982b), involved the formation of defects by
the process of self-compensation analogous to the behavior in partially ionic,
crystalline materials, in which, for example, acceptor-type cation vacancies
might be formed to lower the total energy when donor impurities are incorpo-
rated. Experimental tests of this model of doping have been reported by Kroetz
et al. (1991). It is uncertain, however, how similar such processes in a-Si:H
should be considered as compared to those in crystalline materials, and how
important such self-compensation processes are even in crystalline materials
in view of developments in recent years (Neumark, 1992; Chadi, 1994).
Rehybridized Two-Site (RTS) Model

This model suggests that extrinsic sources are the cause of the existence of
weak bonds in a-Si:H, and that therefore reduction of impurities might result
in material with fewer dangling bonds produced by photoexcitation (Redfield
and Bube, 1990; Redfield, 1991). The RTS model was suggested by the success-
ful description of the DX and related centers in 111-V and 11-VI compounds
by a two-site model for a foreign atom (Chadi and Chang, 1988, 1989a,b),
and is consistent with a number of properties of the dangling bond defects in
a-Si:H. Figure 3.9 illustrates the RTS model; in this case the ground state of a
foreign atom a t a substitutional site has fourfold coordination, and the center
is electronically inert; in the metastable state one bond to a neighboring Si
atom is broken, and the bonds of the foreign atom rehybridize to form three-
fold coordination. A critique of the RTS model includes the fact that the
DX-type center that was used as its basis does not occur in crystalline Si,
and particularly that dangling bond defects in a-Si:H occur in good-quality
undoped material in which the density of impurities (0: 2 x l O I 5 ~ m - C: ~ ,
7-10 x 1015 cmP3, and N: 5 x 1014 ~ m - is ~ much
) less than the density (5 x
of )dangling bond defects (Nakata et al., 1993; Kamei et al., 1996).
1017 ~ r n - ~
Fig. 3.9. A proposed RTS model for the metastable center based on a foreign atom in
analogy with the DX center in crystalline compounds; (a) ground state, (b) metastable
state. (Reprinted with permission from D. Redfield and R. H. Bube, Phys. Rev. Lett. 6 5 ,
464 (1990). Copyright 1990, American Institute of Physics, College Park, MD.)
Carrier-Induced Model
Some of the characteristics of dangling-bond defect formation in a-Si:H do not
appear to fit with the general theme of the above models, i.e. that recombi-
nation energy is the driving force. Typical examples are (a) the formation of
defects in accumulation layers where carrier recombination is negligible, (b)
photoinducing of defects as effectively at temperatures as low as 4 K as at
300 K , and (c) enhancing the annealing rate of excess defects by the addition
of photoexcitation (Street, 1991; Meaudre and Meaudre, 1991a,b; Isomura
and Wagner, 1992; Gleskova et al., 1993a,b). An open-ended proposal has
been advanced (Redfield and Bube, 1996) in terms of the configuration coor-
dinate diagram of Fig. 3.10, which resembles that for the EL2 defect in GaAs
(Dabrowski and Scheffler, 1989).
84 Photovoltuic Materials
QO Q1
(1
00
CONFIGURATION
a, 01 *
Fig. 3.10. (Lower) A proposed configuration-coordinate diagram for a carrier-induced defect-
formation mechanism . It is assumed that the conduction band is higher at a defect than
elsewhere, and that at E3 the latent center on the left can convert t o the defect on the
right with no energy barrier, simply by capture of a carrier from the conduction band.
The photoinduced process starts with t h e excitation of an electron at an existing defect;
the excited electron can move to a latent center t o form another defect. (Upper) Atomic
arrangements at configurations Qo, the latent-defect configuration, and & I , the dangling-
bond configuration. (Reprinted with permission from D. Redfield and R. H. Bube, Phil.
Mug. B 74, 309 (1996). Copyright 1996, Taylor & Francis Ltd., London.)
Discrete Energy Level Models

In spite of the possible complications of the amorphous structure, striking
examples of the success of a discrete energy level model for dangling bond
defects in describing a variety of measurable effects can be cited. It is at
least helpful to think in terms of such a discrete-level model for describing the
electronic behavior of such defects. Such a discrete-level model can readily
be generalized to more complex distributions - for example, discrete levels

corresponding to several different types of multivalent defects, or a Gaussian
distribution of level density with energy, similar t o the top of Fig. 3.8.
Fig. 3.11. Simple discrete-energy-level model for a trivalent defect, such as a dangling bond
defect in a-Si:H, with possible charge states of -, 0, and+. The dashed portion of each defect
level indicates t h e condition in which the level is in its state of lower electronic occupancy.
The arrows represent possible optical or thermal excitation energies, and recombination
energies as described in the text.
Model for a trivalent defect

A representation of such a model for a trivalent defect such as a dangling bond
in a-Si:H is given in Fig. 3.11. The upper level in the gap corresponds to the
negatively charged defect when occupied by two electrons (solid line) and the
neutral defect when occupied by only one electron (dashed line). For the sake
of simplicity in discussion take E, = 0 as the reference energy. To indicate
the dual-charge nature of the energy level, it is designated as lying at E ( - / 0 )
above the valence edge. It is a simplification to put both of these levels at the
same energy, but one that appears to be applicable to covalent semiconductors
such as a-Si:H, as further described below. The lower level corresponds to the
neutral defect when occupied by one electron (solid line) and the positively
charged defect when electron unoccupied (dashed line). Again, to indicate
the dual-charge nature of the energy level, it is designated as lying at E(O/+)
above the valence edge. The model is completed by the inclusion of expo-
nential conduction-band-tail states and valence-band-tail states, but generally
considers only capture transitions involving these recombination centers and
electrons or holes in extended states. The density of trapped electrons or holes

in tail states is calculated simply from the location of the dark or quasi-Fermi
levels; the assigned role of the tail states in this model is therefore to behave
as electron or hole traps.
This model using a single set of discrete energy levels with E(-/O) =
0.90 eV and E(O/+) = 0.45 eV, was reasonably successful in describing the
published variation of photoconductivity with doping (LeComber and Spear,
1986) and changes in photoconductivity versus photoexcitation intensity under
1 2 3 4 5 6 7
DEFECT DENSITY
Fig. 3.12. The Ferrni energy as a function of the defect density (in units of 10l6 and
measured at room temperature) at three different measurement temperatures: 298, 338 and
368 K , for a sample of undoped high-quality a-Si:H. At each of these temperatures data
are plotted from optical degradation versus time runs at 45OC (o), 8OoC (0)95OC ( o ) ,
and llO°C (A). The lines are empirical least-square linear fits to all the data at a fixed
temperature. (Reprinted with permission from R. H. Bube et al., J . A p p l . Phys. 75, 1571
(1994). Copyright 1994, American Institute of Physics.)
optical degradation (Staebler and Wronski, 1980), as well as in providing the

framework for making corrections t o measured defect densities by the constant
photoconductivity method (CPM) because of the change in Fermi energy with
optical degradation (Bube and Redfield, 1989; Bube et al., 1992, 1994; Mettler
et al., 1994; Sauvain et al., 1994; Hubin et al., 1995).
Model with two trivalent defects

A particularly interesting development from attempts to use simple discrete-
level models arises from the consideration of a large amount of data relating
dark conductivity, photoconductivity and defect density measured with a single
sample of undoped, high-quality a-Si:H (Benatar et al., 1992; Benatar, 1993)
as a function of time of optical degradation a t four different temperatures. The
order of events was as follows:
(1) Examples of the empirical relationships shown by the data are given in
Fig. 3.12 (Bube et al., 1994). The results of the analysis show that given
any two of the quantities, Fermi energy, temperature, and metastable de-
fect density, the third is very closely specified, regardless of the history of
the sample. It may be concluded that the defects measured by CPM in
this undoped, high-quality a-Si:H are identical to the defects that control
the Fermi energy.
(2) Fairly stringent conditions are imposed on a simple model that can de-
scribe the above phenomena. No simple model consisting of a single triva-
lent defect is able t o do this, but a model containing two trivalent defects
reproduces the data very well, if their CPM density, as a function of the
total measured defect density, varies as shown in Fig. 3.13. Higher-lying
defects have a density N1 that is relatively constant as the total defect
density increases, whereas lower-lying defects have a density Nz that in-
creases monotonically with total defect density. At 298 K in this model
E1(-/0) = 1.057 eV, El(O/+) = 0.857 eV, Ez(-/O) = 0.965 eV, and
Ez(O/+) = 0.765 eV, where U = 0.2 eV has been arbitrarily chosen for
both defects. Because of the high sensitivity of the results, a small temper-
ature dependence of these energies must be included in the model, which
can be related to the dependence of the Fermi energy on temperature.
A number of other literature references exist in which evidence for
at least two-different kinds of defects are indicated (Bennett et al., 1987;
McMahon, 1992; Sakata et al., 1992; Saleh et al., 1992, 1993; Grimbergen
et al., 1993; Ttan et al., 1993; Zhang et al., 1994).
1 2 3 4 5 6 7
TOTAL DEFECT DENSITY
Fig. 3.13. Calculated variation of the densities (all densities in units of 1OI6 ~ r n - ~of) two
kinds of trivalent defects as the defect densities are increased with optical degradation, as
required to fit the d a t a of Fig. 3.8 using the model of Fig. 3.7 for two kinds of defects. Open
points are calculated for the higher-lying defects, and solid points are calculated for the
lower-lying defects. Measurements of Fermi energy were made at 298 K (o),338 K (O), and
368 K (A). (Reprinted with permission from R. H. Bube et al., J . A p p l . Phys. 75, 1571
(3) Using the two-defect model, the variation with optical degradation of defect
densities, photoconductivity, and Fermi energy was used to obtain informa-
tion about the values of the electron capture cross sections of charged and
neutral dangling bond defects at room temperature. The following values
were obtained: Sy = (1kO.09) x cm2, S: M (0.6k0.05) x cm2,
Sf M (1.8 f 0.5) x cm’, and S: M (18 i 6) x cm2.
These values for capture cross sections are reasonably consistent with
earlier attempts to determine them. Measurements of the neutral cross
sections had indicated values of So M 4 x cm2 (Street, 1982), lo-''

cm2 (McElheny et al., 1991), or at least one order of magnitude smaller
(Pandya and Schiff, 1985); measurements of Sf/So indicated a ratio of
approximately unity (Gunes et al., 1991; Street, 1991), but other reports
indicate S + / S oz 50-100 (Beck et al., 1993, 1996).
10'
7-
'0 4 0
10'
10- 5:-
10- ?--
10- 't
0.5 0.7 0.9 1.1 1.3 1 i
(FERMI ENERGY) - (VALENCE EDGE ENERGY), eV
(4
Fig. 3.14. (a) Variation of the photoconductivity in a-Si:H as a function of the loca-
tion of the Fermi energy as varied by doping. The solid circles are experimental data
from LeComber and Spear (1986), and the open circles are the results of applying the
two-defect model of Fig. 3.13, using a typical variation of total defect density with
doping from Street (1985). (b) Comparison of the measured values of electron lifetime
( x lo-' s) corresponding to optical degradation at 353 K (solid circles ) with the values
of electron lifetime calculated from the two-defect photoconductivity model of Fig. 3.13
using measured total defect densities and the capture cross sections determined as above
(open circles). (Reprinted with permission from R. H. Bube e t al., J . Appl. Phys. 79,
1926 (1996). Copyright 1996, American Institute of Physics.)
0 1 2 3 4 5 6
log t, sec
(b)
Fig. 3.14. (Continued )
(4) Using the two-defect model and the capture cross sections just described,
comparison with different kinds of experimental data showed excellent cor-
relation. Figure 3.14(a) shows the dependence of photoconductivity on
Fermi energy according to the data of LeComber and Spear (1986), which
fits with the two-defect model using typical total defect densities as a func-
tion of doping level from Street (1985), considerably better than for the
single trivalent model mentioned above (Bube and Redfield, 1989). And
Fig. 3.14(b) shows a close fit between the experimental optical degrada-
tion of lifetime at 353 K and the values of electron lifetime calculated from
the photoconductivity model with the two trivalent defects and inferred
capture cross sections.
Amorphous Silacon 91
(5) Finally, it can be shown that sublinear photoconductivity, i.e. Au cx GY

where G is the photoexcitation rate and y < 1, commonly observed at lower
light intensities at room temperature, results directly from an increase in
the density of positively charged defects corresponding to both higher-
energy and lower-energy defects in the two trivalent defect model upon
photoexcitation, the effect of increased defect density being amplified by
the ratio R >> 1 of charged to neutral capture coefficients for the lower-
lying defects.
3.5. Overview of a-Si:H Solar Cells

Summaries of solar cells fabricated from a-Si:H before 1985 are given by Fahren-
bruch and Bube (1983), Chopra and Das (1983), Carlson (1984), Hamakawa
(1985), and Van Overstraeten and Mertens (1986). The photovoltaic effect
was first observed in a-Si:H in 1974 using films deposited by the DC glow-
discharge decomposition of silane (SiH4) and both Schott ky-barrier and pi-n
device structures (Carlson, 1977a). Initial efficiencies were limited to less than
1% because of poor contacts, but by 1976 the efficiency of the p i - n struc-
ture had been improved to 2.4% (Carlson and Wronski, 1976), and in 1977
Fig. 3.15. An energy band diagram for a pi- cell in the short-circuit mode. (Reprinted
from D. E. Carlson, “Solar Cells” in Semiconductors and Semimetals. Vol. 21. Hydrogenated
Amorphous Silicon, Part D. Device Applications, 3 . I. Pankove, ed., p. 7 (1984). Copyright
1984, Academic Press, Orlando, FL.) ’
an efficiency of 5.5% was obtained in a small Schottky-barrier device (Carlson,

197713). It was during this time that the importance of H in the structure,
forming effectively a Si-H alloy, became fully appreciated (Triska et al., 1975;
Connell and Pawlik, 1976). An energy-band diagram for a typical pi-n cell is
given in Fig. 3.15, and schematic diagrams of typical solar cell structures are
given in Fig. 3.16.
El IT0 ( - 7 0 n m )
- - - - - ---
n-LAYER ( - 8 n m )
UNDOPED a-Si’H(-0.5pm)
p-LAYER (-20nm)
_-__--
STEEL
(b)
----
Fig. 3.16. (a) A pi-n solar cell structure on a glass substrate. (b) A pi+ solar-cell
structure on a steel substrate. (c) A stacked or multijunction structure where the i* layer is
a narrow-band-gap alloy such as a-Si:Ge:H. (Reprinted from D. E. Carlson, “Solar Cells” in
Semiconductors and Semimetals. Vol. 21. Hydrogenated Amorphous Silicon, Part D. Device
Applications, J. I. Pankove, ed., p. 7 (1984). Copyright 1984, Academic Press, Orlando, FL.)
- hv
GLASS
...
1 I l l 1
t t t t t
' i np i' n
(c)
Continued improvements in deposition conditions led to an initial efficiency

of 6.1% in pi-n cells by 1980 (Carlson, 1980), to 7.5% in 1981 using a p
type layer window-layer that was a larger-bandgap, boron-doped a-Si:C:H al-
loy (Tawada et al., 1981) and then to 10.1% in 1982 with a similar struc-
ture (Catalan0 et al., 1982). The output parameters for this 1.09 cm2 cell
were qhoc = 0.84 V, J,, = 17.8 mA/cmP2, and f f = 0.68. Boron doping of
a-Si:H results in increased absorption and lower carrier lifetime, leading to
a loss in photoinduced current; alloying the a-Si:H with C to produce an
a-Si:C:H p-type layer decreases this effect, as shown in Fig. 3.17(a). A stacked-
junction structure using a smaller-bandgap a-Si:Ge:H alloy in the back junc-
tion of three stacked pi-n junctions gave an efficiency of 8.5% (Nakamura
et al., 1982). The output parameters for this 0.09 cm2 cell were qhoc = 2.2 V,
J,, = 6.74 mA/cm-', and ff = 0.57. Optical absorption spectra comparing
a-Si:H, a-Si:Ge:H, and a-Si:C:H are shown in Fig. 3.17(b).
A general summary of solar cells utilizing a-Si:H is given in Fig. 3.18
(Maruyama et al., 1995). They include (a) the standard all a-Si:H p-i-n
structure, (b) replacement of the p t y p e a-Si:H by p t y p e a-Si:C:H, (c) tex-
tured transparent conducting coating for better optical absorption, (d) use of
a graded p t y p e a-Si:C:H layer, ( e ) two-cell tandem p-i-n all a-Si:H struc-
ture, ( f ) three-cell tandem pz-n cell structure using larger band gap a-Si:N or
a-Si:C and smaller bandgap a-Si:Ge or a-Si:Sn, (g) two-cell tandem using a n
Fig. 3.17. (a) Optical absorption as a function of photon energy for undoped a-Si:H (solid
curve), p t y p e a-Si:H (dashed curve), and p t y p e a-Si:C:H (dashed-dotted curve.) Both
p t y p e films contain a few atomic percent of boron, and the a-Si:C:H film also contains
20 at. % of carbon. (b) Optical absorption coefficient as a function of photon energy for
a-Si:H, a-Sio.ls:Geo.sz:H (von Roedern et al. 1982), and a-Sio.7~:Co.zs:H(Morimoto et al.,
1982). (Reprinted from D. E. Carlson, "Solar Cells" in Semiconductors and Semimetals.
Vol. 21. Hydrogenated Amorphozls Silicon, Part D. Device Applications, 3 . I. Pankove, ed.,
p. 7 (1984). Copyright 1984, Academic Press, Orlando, FL.)
(a) D i n structure
..
(b)p-SiCh n a-SiN a-SiSn
a-SiC a-SIGe
n
(c) Textured TCO
6 (d) a-Sic graded

interface layer
< Single junction > < Multijunction >
Fig. 3.18. Schematic structure of a variety of cells involving a-Si:H. (Reprinted with permis-
sion from E. Maruyama et al., Solid State Phenomena 44-46, 863 (1995). Copyright 1995,
Scitec Pub., Switzerland.)
a-Si:H p i - n cell in tandem with a microcrystalline Si p n cell, (h) so-called

“Heterojunction with Intrinsic Thin Layer” (HIT) between p and i-type a-Si:H
and n-type crystalline Si, and (i) two-cell stacked tandem using a p i - n a-Si:H
cell in tandem with a CuInSe2 cell. Variations of the transparent conducting
oxide (TCO) layers that are used in all of these cells led to the proposal of
a composite TCO consisting of glass/SnOZ:F/TiOz:Nb as a good electrical
contact for a-Si:H solar cells (Hegedus et al., 1995).
For single-junction solar cells, recent progress has increased the initial effi-
ciency to 13.2% (Miyachi et al., 1992) and the stabilized efficiency after long-
time optical exposure to 8.5% (Xi et al., 1994) or 8.8% (Hishikawa et al.,
1994). These more advanced cells include such efficiency-enabling features as
composition-graded layers, multilayers, and optical coatings to increase light

absorption (Schropp, 1995). With the use of thinner undoped absorbing lay-
ers of a-Si:H, multijunction a-Si:H-based solar cells using a-Si:H alloys have
achieved a stabilized efficiency of over 10% (Nomoto et al., 1993; Arya et al.,
1993; Guha et al., 1993).
A significant development has been the fabrication of a-Si:H solar cells on
a thin, flexible, stainless steel substrate, making possible a continuous “roll-to-
roll” manufacturing technology (Izu et al., 1983, 1993, 1994; Ovshinsky 1988;
Nath et al., 1988). This process benefits from the mechanical strength of the
stainless steel, transport of modules during manufacturing is simple and less
expensive, and heating and cooling of the substrate during deposition can be
achieved quickly. An a-Si:H solar cell with a plastic film substrate has also
been described (Ichikawa et al., 1994; Kuo et al., 1994, Shinohara et al., 1994).
A detailed summary of some sixteen optimization techniques is given by
Schropp (1995) to increase the initial efficiency, increase stability, achieve opti-
cal enhancement, and optimize tandem structures. A review of the physics and
technology of a-Si:H solar cells and modules is given by Kusian (1995). Con-
sideration of seven research areas for the improvement of solar cell efficiencies
using amorphous semiconductors is given by Paul et al. (1993).
3.6. Variations in Deposition Techniques

General information on the deposition and structure of a-Si:H films can be
found in several chapters in Vol. 21A of the book edited by Pankove (1984),
and in six review papers in the volumes edited by Neber-Aeschbacher (1995).
Although a variety of techniques were used t o grow a-Si:H films for solar cells
(Carlson, 1984), the highest-efficiency cells were made from films grown in
radio-frequency (rf) glow discharges in SiH4 using a p t y p e a-Si:C:H layer
(Catalan0 e t al., 1982). Comparable performance was reported for cells made
from glow discharges in silicon tetrafluoride (SiF4) and hydrogen (Madan and
Ovshinsky, 1979; Hack and Shur, 1982).
Other deposition techniques that were early investigated include DC glow
discharge in SiH4 (Uchida, 1984), chemical vapor deposition (CVD) using SiH4
and also higher-order silanes such as Si2H6 (Dalal, 1982), and homogeneous
CVD (HOMOCVD) (Scott et al., 1981). Sputtered a-Si:H films have been
investigated but the density of defects is sufficiently high that cells made from
sputtered films have only limited efficiency (Anderson et al., 1977; Moustakas
et al., 1977). Heterojunction solar cells were fabricated by DC magnetron
sputtering of a-Si:H from an n-type Si target, onto p t y p e single-crystal Si,
with an efficiency of 10.7% (Jagannathan and Anderson, 1996).
The glow-discharge decomposition of silane remains the standard deposi-

tion procedure for a-Si:H. A variety of other methods have also been tested
in recent years. (a) Shah et al. (1988), Finger et al. (1992) and Kroll et al.
(1992) explored a very high frequency (VHF) glow discharge as a high rate
deposition method for a-Si:H using plasma excitation frequencies in the range
of 70-100 MHz compared to the standard frequency of 13.6 MHz. The higher
frequency increases the deposition rate by a factor of three to five to 1.2 to
1.5 nm/sec, without reducing film quality. The use of this method for the
production of pc-Si:H films was discussed in Sec. 2.8. (b) Fabrication of a-Si:H
pi-n solar cells by CVD using disilane has been reported (Hegedus et al.,
1987), but they exhibit a rather low efficiency of 4%0,limited by the quality
of the intrinsic CVD material. (c) Materials more nearly equivalent to stan-
dard a-Si:H have been deposited by photo-assisted CVD (Hegedus et al., 1988;
W. Y. Kim et al., 1988a,b). (d) Device quality a-Si:H was also reported as
deposited by DC magnetron reactive sputtering (Pinarbasi ei! al., 1988) with
deposition rates of 0.055 to 0.33 nm/sec. (e) High quality i-layers of a-Si:H
were deposited with the hot-wire deposition technique (Nelson et al., 1994;
Mahan et al., 1996), and also were incorporated into p i - n solar cells.
An attempt to modify reactions a t the growing a-Si:H surface through the
use of an inert gas plasma treatment, using rf plasma CVD, has been investi-
gated (Maruyama et al., 1996). It appears that the inert gas plasma treatment
reduces the hydrogen content, promotes the rearrangement of the Si-network,
and reduces the ratio SiHZ/SiH. High-quality films have been produced with
a high, stabilized photoconductivity.
3.7. M a t e r i a l Transport P r o p e r t i e s Important f o r Solar Cells

A discussion of electronic structure and transport properties in a-Si:H is given
in eight review papers in the volumes edited by Neber-Aeschbacher (1995). In
a-Si:H pi-n solar cells, collection of photoexcited carriers near short-circuit
conditions is primarily by drift in a built-in electric field E, and high efficiency
requires a drift length ( ~ T Eseveral
) times larger than the film thickness, where
p is the carrier mobility, T the carrier lifetime, and E the electric field in the
i-region. Crandall (1982) proposed that transport in p i - n solar cells can be
characterized by a collection length that is the sum of the electron and hole drift
lengths. In short-circuit conditions, the collection length is typically 2 5 pm
in the short-circuit mode and decreases as the cell goes into forward bias,
while transport by diffusion dominates as the cell approaches the open-circuit
98 Photovoltazc Materials
condition. High efficiency requires a diffusion length several times larger than
the thickness of the active region, which in turn requires a mobility lifetime
product p r > cm2V-' for a thickness of 0.5 pm, a condition that is met
in good-quality a-Si:H.
Large diffusion lengths in a-Si:H require a low density of defect states in the
gap. Such defects are most commonly associated with dangling-bond defects
as described in Sec. 3.4. They may arise during film growth by hydrogen out-
diffusion (Fritzsche et aZ., 1978), or may be associated with microstructural
imperfections such as polymer chains (Knights et al., 1979), or with impurities
such as oxygen (Pontuschka et aZ., 1982) and carbon (Morimoto et al., 1982). It
has been suggested that transport in a-Si:H may be strongly affected by inho-
mogeneities that give rise to potential fluctuations (Overhof and Beyer, 1981).
Metastable dangling-bond defects formed by photoexcitation (see Sec. 3.4) also
decrease the diffusion length.
High doping levels in the n- and p-type layers of a pi- a-Si:H solar cell
are desired to order to obtain a large built-in potential, approaching the band
gap in magnitude. Such high doping levels, however, are limited both by the
existence of the band-tail states and by low doping efficiency in a-Si:H, pre-
sumably because most dopant atoms do not occupy electronically active sites.
Estimates of the doping efficiency are in the range of 0.1 to 1.0% (Faughnan
and Hanak, 1983; Dresner, 1983). The Fermi level is about 0.2 eV below the
conduction band in a-Si:H:P (Spear, 1977) and about 0.5 eV above the valence
band in a-Si:H:B (Jan et al., 1980), limiting the built-in potential of a-Si:H
pi-n solar cells to about 1.0 eV (Williams et al., 1979). This built-in po-
tential is increased by using p-type a-Si:C:H layers (Tawada et d., 1982), but
the resistivity of the layer increases with the band gap, i.e. with the C/Si ra-
tio. The conductivity of the p-type layer in a boron-doped a-Si:H layer can be
significantly increased by forming microcrystalline-doped Si:H films (Matsuda
et al., 1980) but without significant increase in the built-in potential (Carlson
and Smith, 1982). The n-type layer can also be improved by making it micro-
crystalline (see Sec. 2.8), which is formed if the silane gas is heavily diluted
with hydrogen (Smith, 1991). The microcrystalline material has a higher con-
ductivity than a-Si:H, thus reducing resistive loss and improving the fill factor.
Under the assumption that the electric field in the i-layer is almost uniform,
if both the trapped charge and the free-carrier space charge are assumed to be
negligible, a simple model was developed that related the fill factor of pi-n
cells to the collection length (Crandall, 1982; Faughnan and Crandall, 1984)
with the results shown in Fig. 3.19. They found that the collection length at
,-
--
I I L
01 1 .o 10 100
Lc /d
Fig. 3.19. Dependence of the fill factor as a function of collection length for a-Si:H p i - n
cells. Comparison of theoretical variation (dashed line) and experimental points on a number
of pz-n solar cells. (Reprinted with permission from B. W. Faughnan and R. S. Crandall,
Appl. Phys. Lett. 44, 537 (1984). Copyright 1984, American Institute of Physics.)
short-circuit must be 25 times the i-layer thickness to obtain a fill factor of

0.72. In many low-performance a-Si:H cells, the net space charge in the i-layer
is not negligible] and a quasi-neutral region is present in the central portion
of the i-layer, resulting in depletion regions or space-charge fields near the pi
and i-n interfaces and loss of photoexcited carriers by recombination.
One of the transport properties of a-Si:H of interest for solar cells is the in-
terpretation of the mobility-lifetime] p ~product.
, A problem was raised by the
observation that the p r product deduced from steady-state photoconductiv-
ity is about 100 times larger than the p r product deduced from time-of-flight
charge collection . This conflict was apparently resolved (Kocka et al., 1991)
by the proposal that the p r product deduced from time-of-flight measurements
is the result of single-carrier, trap-limited transport] whereas the p r product
deduced from steady-state secondary photoconductivity is a two-carrier] re-
combination limited quantity.
The investigation of the interpretation of the p r product in a-Si:H has
been continued with a combination of steady-state photoconductivity, time-
of-flight] and steady-state photocarrier grating measurements (Wyrsch et al.,
1995; Beck et al., 1996). They define a correlation quantity p0-ro,deducible
from combining steady-state photoconductivity and steady-state photocarrier
grating measurements, which corresponds to the value of the p r product when

all the defects in the material are neutral and therefore does not depend on the
actual dangling bond occupation in the measured sample. The values of the
p o r Oproducts evaluated on films are reported to correlate with the efficiencies
of corresponding solar cells.
3.8. Solar Cell Stability

In spite of the promise and initial high efficiency of a-Si:H solar cells, their
widespread use has been slowed by the decrease in their efficiency with time
of photoexcitation. Most solar cells of a-Si:H lose about 30% of their gener-
ating capacity and must be derated accordingly. Typical dependence of ef-
ficiency on time for cells of the types shown in Fig. 3.16(a) and 3.16(b) are
given in Fig. 3.20. The efficiency can be recovered by thermally annealing the
AM1 EXPOSURE ( h r )
Fig. 3.20. Efficiency as a function of exposure time to AM1 radiation for a-Si:H solar cells.
Curves A and B are data for cells of the type shown in Fig. 3.16(a), and curve C is for a cell
of the type shown in Fig. 3.16(b). For curves A and B, the p t y p e region was a-Si:C:H, with
the carbon content for curve B (1.7 x lo2* ~ m - ~ being
) about 100 times larger than that
associated with curve A. (Reprinted from D. E. Carlson, “Solar Cells” in Semiconductors
and Semimetals. Vol. 21. Hydrogenated Amorphous Silicon, Part D. Device Applications, J.
I. Pankove, ed., p. 7 (1984). Copyright 1984, Academic Press, Orlando, FL.)
a-Si:H cells at about 200°C for several minutes. It was reported early that the
decrease in a-Si:H solar cell efficiency with time of photoexcitation was similar
to the formation of metastable defects in thin film a-Si:H under photoexcitation
(Staebler et al., 1981). The formation of new defects by exposure to light
decreases the lifetime, diffusion length, and drift length. It was also found
that the net space charge often increases with photoexcitation (Carlson et al.,
1983), contributing by itself to a decrease in efficiency.
4.0.
-2 3.0.
>
u
2.0'
-
0
LL
& 1.0
0.0 '
I
0
- .-
200
.
400 600
I . LAYER THICKNESS (nrn 1
Fig. 3.21. Photovoltaic parameters as a function of the thickness of the i-layer in p i - n

cells before (A) and after (0)67 hours of exposure t o AM1 illumination. (Reprinted with
permission from J. J. Hanak and V. Korsun, 16th IEEE Photovoltaic Specialists Conference,
p. 1381 (1982). Copyright 1982, IEEE, NY.)
Three significant observations may be noted (Staebler et al., 1981):

(a) photoinduced degradation of a p i - a-Si:H solar cell can be reduced by
operating the cell short-circuit rather than open-circuit, and can be prevented
by applying a reverse bias to the cell during photoexcitation; (b) consistent
with this is the observation that photodegradation is reduced in cells with
thinner i-layers since the electric field in the i-layer is increased; and (c) cells
degrade similarly in the dark under forward current flow.
Point (b), the dependence of cell stability on i-layer thickness, is illustrated
by Fig. 3.21 (Hanak and Korsun, 1982). No degradation is observed in p i - n
cells with thin i-layers, but when the i-layer thickness exceeds 0.2 pm, all the
photovoltaic parameters exhibit some degradation, particularly the fill factor.
A variety of at least partly effective methods have been used to reduce
the optical degradation effects in a-Si:H solar cells (Maruyama, 1995). These
include the reduction of impurities such as oxygen and nitrogen (Tsuda et al.,
1995), the reduction of Si-HZ bonds in the a-Si:H film (Kuwano et al., 1987), a
multijunction structure with thin i-type a-Si:H layers (Nakamura et al., 1985),
a tandem structure using blocking layers (Ichikawa, 1990), the use of “hot-
wire” deposition techniques resulting in a lower hydrogen concentration and an
altered microstructure (Vanecek et al., 1992), the use of hydrogen-diluted silane
([H2]/[SiH,] = 10) in the rf-PECVD deposition of a-Si:H layers (Lee et al.,
1996), and the use of hydrogen electron-cyclotron-resonance (ECR) plasma-
CVD growth techniques (Dalal et al., 1994, 1996).
An investigation of the light-saturated defect density in a-Si:H as a function
of oxygen content, microstructure and hydrogen bonding, indicated no increase
in stability with decrease in the concentration of oxygen down to 5 x 1017~ m - ~ ,
but an increase in stability with a decreased hydrogen content due to a change
in material microstructure (Haage et al., 1994; Vanecek et al., 1995).
A comprehensive study of solar-cell degradation was carried out by Chen
and Yang (1991). Their data on the efficiency of a-Si:H solar cells as a function
of time of photoexcitation are shown in Fig. 3.22 with fits t o their data using
stretched exponentials with essentially the same parameters as those which ap-
ply to defect densities in undoped, homogeneous films. This is one of several
indications that the optical degradation of a-Si:H solar cells is dominated by an
increase in the density of metastable defects in the i-layer of the cells, thus de-
creasing the carrier lifetime and possibly causing other effects directly related
to the density of defects, such as a decrease in carrier mobility or a change in the
field distribution in the cell. Recent data comparing the effects of optical degra-
dation in films of a-Si:H and solar cells based on a-Si:H have been discussed
I I
10’ 102 Id 1o4
Time (sec)
Time (sec)
(b)
Fig. 3.22. Efficiency of a-Si:H solar cells as a function of time of exposure t o light. Points
are the measured efficiencies, normalized t o their initial values, and curves are fits t o the
data using stretched exponentials. In (a) a fixed intensity of 140 suns was used with various
temperatures, whereas in (b) and (c) fixed temperatures of 5OoC and 100°C, respectively
were used with various intensities. (Reprinted with permission from L. Chen and L. Yang,
J. Non-Cryst. Solids 137/138,1185 (1991). Copyright 1991, North-Holland, Amsterdam.)
} T=lOo'C -P-
101 102 id 104 105 lo6

Time (sec)
(c)
Fig. 3.22. (Contznued )
(Redfield and Bube, 1991), based on annealing kinetics, existence and proper-
ties of saturation, degradation kinetics, thickness dependence of degradation,
and performance modeling of films and cells, with the conclusion that degra-
dation in a-Si:H solar cells is an i-layer effect directly related t o the formation
of metastable defects.
A number of other investigations have concluded that the degradation of
solar cell performance is directly related to the increase in the density of
metastable defects under illumination. (1) The relationship between fill factor
and carrier collection length shown in Fig. 3.19 has been tested by relating the
collection length to the defect density, with the result that changes in solar cell
performance due to changes in fill factor are directly correlated with defect
density (Frammelsberger e t al., 1991). (2) A computer model of cell degrada-
tion (Pawlikiewicz et al., 1991) showed good correlation between measured fill
factor and bulk defect density. (3) A comprehensive computer model of simi-
lar Schottky barrier MIS cells, for different i-layer thicknesses and durations of
light exposure, showed good agreement between observed degradation and cal-
culated quantum efficiency spectra based on the density of defects only (Malone
e t al., 1991). (4) Measurements of efficiency versus time of optical degradation
for large monolithic solar-cell modules involving a-Si:H show behavior quite
similar to that for films and single cells (Luft et al., 1991). (5) Optical degra-
dation at 60°C and modeling of a-Si:H pz-n cells well into saturation of their
conversion efficiency were interpreted to mean that the light-induced defects in

the i-layer control the optical degradation of pi-n cells (Wagner et al., 1991).
(6) An investigation of pi-n and n-i-p solar cells after optical degradation,
current injection and keV-electron irradiation led to the conclusion that the
degradation of the i-layer bulk is the dominant effect in the optical degrada-
tion of such cells (Herbst et al., 1993). ( 7 ) At least as far as a-Si:H deposited
by the VHF method (see Sec. 3.6) is concerned, the electron and hole drift
mobilities remain unchanged near room temperature by light-induced degra-
dation (Wyrsch and Shah, 1991). This result contradicts the suggestion that it
is long range potential fluctuations that affect the electron mobility and limit
solar cell performance, rather than the increase in the density of deep defects
(von Roedern and Madan, 1991). (8) Experiments focusing on the p / i inter-
face and designed to separate interfacial from bulk defect-related degradation
indicated that optical degradation effects can be modeled without including
any interfacial losses (Vasanth et al., 1994). (9) By means of a n extensive
characterization of bifacial a-Si:H solar cells, using a well-defined sequence of
degradation steps, and using alternatively both strongly absorbed and uni-
formly absorbed light, it was concluded that optical degradation is controlled
mainly by an increase of the deep defect density in the bulk of the i-layer
(Wyrsch and Shah, 1994).
Still disagreements about basic degradation mechanisms exist. As indi-
cated above, some of these have been addressed in recent research and shown
to be probably inapplicable. (1) Evidence has often been advanced that other
phenomena, e.g. interfacial recombination effects a t the pi or i-n boundaries,
are responsible for at least some of the degradation (Mitchell et al., 1985).
( 2 ) Some research indicates contributions to degradation both from defects
in the i-layer and at the p / i interface (Li et al., 1992). (3) A comparison of
current-induced and light-induced defects in a-Si:H indicates that the same
dangling bond defects are formed in pi- diodes by the two techniques, but
optical excitation forms a high density of defects close to the pi interface, while
current flow yields a more uniform distribution (Street et al., 1993). (4) Analy-
sis of thin film stability by itself does not adequately correlate with the stability
of solar cells involving such films (Schropp et al., 1993). (5) Improvement in
the stabilized efficiency of a-Si:H solar cells has been reported by profiling the
i-layer of the solar cell to prevent a modification of the spatial electric field
distribution upon photoinduction of defects (Schropp et al., 1993a,b, 1994).
(6) Reports have been made of cases where materials with lower spin-deter-
mined defect densities do not automatically produce better solar cells (von
Roedern et al., 1992), and it is proposed that solar cell performance is
determined and limited by the density of charged dangling bonds that are not
measured by ESR (von Roedern, 1993). (7) Significant differences in the stabi-
lized performance are reported depending on the conditions used to illuminate
a-Si:H multijunction modules (von Roedern et al., 1995). (8) Empirically a
relationship has been found between a greater electric field dependence of the
drift mobility (pd increases with electric field) of a n a-Si:H film in the annealed
state and a poorer stability of the photoconductivity upon photoexcitation
(Tang et al., 1996). (9) Along with the decrease of photoconductivity and
lifetime during exposure t o light, a continuous decay of the drift mobility was
also found, suggesting enhanced scattering associated with charged optically
induced defects (Tang and Braunstein, 1996). It is reported that different gen-
eration kinetics are measured using stretched-exponential kinetics for defects
leading to increased recombination (decrease of lifetime) and those leading to
decrease of drift mobility.
3.9. Amorphous Silicon Alloys

As pointed out elsewhere in this chapter, alloys of a-Si:H, particularly with
C or Gel play a n important role in the overall solar-cell development picture
(Bauer, 1995; Demichelis and Pirri, 1995). A review of deposition processes
for amorphous silicon alloys is given by Luft and Tsuo (1993).
The performance of a-Si:Ge:H solar cells were investigated as a function
of the band gap between 1.2 and 1.7 eV, with the finding that the solar cell
performance drops sharply if the band gap is smaller than 1.5 eV (Smith et al.,
1987). Such a decrease in performance with increasing Ge/Si ratio may be due
to simply the decrease in band gap, or it may be intensified by an increase
in defect density or a widening of the valence band tail with increasing Ge
(Turner et al., 1987).
Variations have been made in the doping of the p t y p e a-Si:C:H window
layer of the a-Si:H p-i-n solar cell. Mohring (1987) replaced the standard use
of diborane in the doping of the p t y p e layer, and substituted plasma assisted
B diffusion from thin SiB-layers on the substrate into the growing intrinsic
film with promising results reported. Ouwens et al. (1994) deposited a high
band-gap p+-a-Si:C:H layer without deteriorated electronic properties using
trimethylboron as a dopant gas.
Investigation indicates that improvements are achieved by introducing
doped microcrystalline Si (pc-Si) and its carbon alloys (pc-Si:C) a t the T C O / p
a-Si:C interface, resulting in an increase in the built-in potential (Ma et al.,
1994; Sannomiya et al., 1994; Rath et al., 1996).
Shibata et al. (1988) used the technique of “&-doping”to increase the peak
boron concentration to 2 x loz1 cmP3 in the p t y p e layer, with apparently
beneficial results, producing a cell with initial efficiency of 11.5% The &doped
player consists of one or several very thin boron layers (0.1 to 0.5 atomic layer)
and undoped a-Si:H layers.
Measurements of electron transport and recombination (Nebel et al., 1988a;
Bauer et al., 1988), and diffusion lengths from optical grating techniques (Nebel
et al., 1988b) on a-Sil-,:Ge,:H alloys have been reported for values of z be-
tween 0 and 0.3. It is reported that the electron mobility in a-Si:Ge:H decreases
with increasing hydrogen concentration and germanium concentration (Fort-
mann et al., 1991). Capacitance techniques have been applied to investigate
the midgap density of states in a-Si:H and a-Si:Ge:H p i - n solar cells and
Schottky junctions (Hegedus and Fagen, 1992).
Optical degradation has been observed for a-Si:Ge:H films (Aljishi et al.,
1987) with effects depending on the band gap of the alloy. If the band gap is
larger than 1.4 eV, an increase in subgap absorption, a decrease in photocon-
ductivity, and a decrease in dark conductivity with an increase in activation
energy was observed. For band gaps less than 1.4 eV, an increase in subgap
absorption, constant photoconductivity, and an increase in dark conductivity
with a decrease in activation energy was observed. Chu et al. (1988) carried
out a similar investigation concentrating on band gaps between 1.2 and 1.4 eV
of interest for multijunction cells.
Variations in deposition techniques have also been tested with a-Si:Ge:H
alloys. Weller et al. (1987) used dc-glow discharge, and Hegedus et al. (1988)
used photo-assisted CVD.
Of particular interest is the series stack of two or three solar cell junctions
with alloys a-Si:C:H with larger band gap, a-Si:H itself, and a-Si:Ge:H with
smaller band gap, shown in Fig. 3.18(f) and in more detail in Fig. 3.23. Since
the i-layer thickness in these cells is narrower than in a simple a-Si:H cell,
it is expected that optical degradation effects would be reduced. Offsetting
this gain is the apparent increased instability of a-Si:C:H compared to a-Si:H,
and uncertainty about the apparent decreased instability of a-Si:Ge:H alloys
because of cited evidence that there is a lack of correlation between defect
density in the bulk and stability of these devices (Xu et al., 1993). Still,
research on the effects of H, Si, and Ge in alloy films has been used to produce
what is claimed to be the most stable a:Si:Ge:H solar cell (Terakawa et al.,
1994). A variety of approaches are being considered to achieve more stable
multijunction cells (Haku, 1991; Maruyama et al., 1993a,b; Hishikawa et al.,
1994; Sayama, 1994).
5 light
a-Si -/
Fig. 3.23. More detail on the device structure of an a-Si:C:H/a-Si:H/a-Si:Ge:H multijunction

solar cell shown in Fig. 3.18(f). (Reprinted with permission from D. E. Carlson and S.
Wagner, in Renewable Energy: Sources for Fuels and Electricity, T. B. Johansson et al.,
eds., p. 403 (1993). Copyright 1993, Island Press, Washington, D.C.).
Properties of a-Si:H/a-Si:Ge:H quantum-well multilayers have also been

investigated, with the demonstration that the optical and transport properties
of such multilayers can be tuned over a wide range by varying the geometry
of the multilayer, without changing the chemical composition of the individual
layers (Conde et al., 1994).
Although not strictly an alloy, mention may well be made a t this point of
attempts to make a red-sensitive a-Ge:H solar cell (Kusian et al., 1991). Im-
provements were achieved by increasing the substrate temperature, decreasing
the pressure during deposition, reducing the i-layer thickness and using a p
Si:C/p+-S front layer, but the final result was still only a 2% cell ($,,= = 0.26 V,
JSc = 16 mA/cm2, ff = 0.47). A limiting factor seemed to be the relatively
high density of defects, of the order of 9 x 10l6 ~ m - ~ .
3.10. Hybrid Solar Cells Involving a-Si:H
Types of heterojunction solar cells involving both a-Si:H and other forms of Si
promise increased efficiency.
Tandem Cell with Multicrystalline Si

In the tandem cell configuration, an a-Si:H/mc-Si heterojunction cell has been
investigated as a bottom cell structure (Hamakawa et al., 1983). Its advantage
is that it does not require high temperature processing for junction formation,
and the top a-Si:H cell can be fabricated continuously. A (p-type a-Si:H/
n-type mc-Si) heterojunction, with a 10 pm thick mc-Si film fabricated by
solid phase crystallization yielded an efficiency of 8.5% (Matsuyama, 1994).
A high-efficiency a-Si:H/mc-Si four-terminal tandem solar cell has been
developed using a ppc-Si:C/n-mc-Si/n-pc-Si heterojunction bottom solar cell
with a conversion efficiency of 20.3% and good stability. (Yoshimi et al., 1992)
Tandem Cell with Microcrystalline Si

It has been reported that microcrystalline (pc) Si:H p-i-n junctions have an
extended infrared response, and are entirely stable under photoexcitation with
an efficiency of 7.7% (Fischer et al., 1996). The tandem arrangement of an
a-Si:H solar cell with a pc-Si:H solar cell also appears promising A remaining
problem is the insufficient deposition rates for the pc-Si:H layers.
Heterojunction with Intrinsic Thin Layer (HIT)

Figure 3.18(h) shows a typical HIT structure. A thin undoped a-Si:H layer
(5 nm thick) is inserted into the p-n junction in order to reduce the density
of states near the interface. A conversion efficiency of 20% has been achieved
with a single crystalline silicon (c-Si) wafer using a low-temperature process.
Multijunction Cells with CuInSe2

There have been several investigations of a multijunction involving an a-Si:H
solar cell and a CuInSe2 solar cell (Mitchell et al., 1988; McCandless, 1988)
as in Fig. 3.18(i). Figure 3.24 shows the solar cell structure for a 14.2% effi-
cient a-Si:H/CuInSez multijunction four-terminal cell (Morel, 1988). Thin film
tandem modules with 0.4 m2 area have been reported with 41.5 watt and an
efficiency of 10.5% (Mitchell et al., 1990).
1 1 1 1 1
. \ ,-
TCopper
7 Indium
Diselenide
Glass
Fig. 3.24. Solar cell structure for a 14.2% efficient multijunction cell consisting of an a-Si:H
pin cell and a ZnO/CdS/CuInSe2 cell. (Reprinted with permission from D. L. Morel,
Solar Cells 24, 157 (1988). Copyright 1988, Elsevier Sequoia S. A., Lausanne, Switzerland.)
CHAPTER 4
GALLIUM ARSENIDE AND OTHER

111-V MATERIALS
4.1. Overview
It is useful to place gallium arsenide and other 111-V materials relevant to solar
cell applications in the context of the Periodic Table of the Elements and their
relationship to the element silicon that formed the basis for the previous two
chapters. A pertinent subsection of the Periodic Table is shown in Fig. 4.1.
Noting the usual trend that elements and compounds have increasing ionic
binding and band gaps as the rows lie higher in the periodic table, and as the
difference between the columns increases, we see the effect described in the
previous chapter that the band gap of Si, in the same column as Ge but lying
5B 6C 7N 8 0
1 3 A Y i y P 1 6 s
29 Cu 30 Zn 31 Ga 32 Ge 33 As 34 Se
47 Ag 48 Cd
/In 49 50 Sn 51 Sb
\ Te 52
79 Au 80 Hg 81 T1 82 Pb 83 Bi 84 Po
Fig. 4.1. A subsection of the Periodic Table of the elements showing the relationship between
Group IV elements like Si and Ge, Group 111-V compounds like GaAs and InP, and Group
IILVI compounds like CdTe.
111
one row higher, is greater than the band gap of Ge. GaAs consists of Ga in
the column to the left of Ge, and As in the column to the right of Ge, giving
rise to a band gap in GaAs, from these considerations only, which is greater
than that of Ge, and would be expected to be more like the band gap of Si.
Actually, since GaAs is a direct-band gap material, its band gap (1.43 eV)
is somewhat larger than that of crystalline Si (1.1eV) with an indirect band
gap. It may be concluded, therefore, that GaAs and InP (which makes up for
In lying in a lower row than Ga, by P lying in a higher row than As) are the
111-V compounds most like Si. We note in passing that if we extend our choice
diagonally down to the left from Si through Ga, we reach Cd, and if we extend
our choice diagonally down to the right from Si through As, we reach Te; we
recognize the fact that CdTe is the major 11-VI material of interest for solar
cells, as discussed in Chapter 5 .
t
ci
d
5.4 5.6 5.0 6.0 6.2 6.4
Lattice Constant, Angstroms
Fig. 4.2. Summary of band gaps and lattice constants for a number of zincblende 111-V com-
pounds, compared with diamond structure Si and Ge, and zincblende ZnTe, CdTe, and HgTe.
Gallium Arsenide and Other III-V Materials 113
The direct band gap of GaAs is near the optimum for solar conversion, as
shown in Fig. 1.2, and leads to 97% absorption of AM1 radiation in a thickness
of about 2 pm. Its higher carrier mobilities than Si allow the fabrication
of high-frequency devices, and it forms a variety of lattice-matched ternary
compounds allowing for controlled variations of properties. GaAs solar cells
should be operable at higher temperatures than silicon cells, and since they
may be very thin, GaAs solar cells are expected t o be radiation resistant. The
band gap versus lattice constant relationship is given in Fig. 4.2 for eight 111-V
compounds with zincblende structure, as well as for a few other semiconductors
for reference such.as Si and Ge with the diamond structure, and ZnTe, CdTe
and HgTe with zincblende structure. For example, Fig. 4.2 shows the close
lattice match between AlAs, GaAs and Ge for three materials with a wide
range of band gaps, as well as for AlSb, GaSb and InAs.
Fig. 4.3. Typical heteroface or buried homojunction p+-AlGaAslpGaAsln-GaAs solar cell

band structure.
As a simple p n junction material, GaAs is handicapped first by the fact

that its high absorption coefficient leads to high carrier photoexcitation rates
near the front surface, which is characterized by high surface recombination
losses. Second, its direct band gap leads to a short bulk lifetime because of
intrinsic recombination processes. The formation of a pAlGaAs/pGaAs/n-
GaAs heteroface (or buried homojunction) structure with the larger band gap
AlGaAs alloy, as shown in Fig. 4.3, however, greatly decreases the recombina-
tion at the front surface of the p G a A s because of the excellent lattice match
between GaAlAs and GaAs (only 0.16% mismatch between AlAs and GaAs).
c
z
W
0
a
W
n
>.’
0
z
w
0
LL
LL
W
Fig. 4.4. Representative values of GaAs-based solar cell efficiency as a function of year.
Three types of cells are included: ( 0 ) homojunction, (m) heteroface (buried homojunction)
without concentration, and (A) heteroface with concentration. Details are discussed further
in Sec. 4.3.
Efficiencies of GaAs-based solar cells are among the highest of any solar
cells, lying between 20% and 30%. Representative values of efficiency as a
function of year and type of cell are plotted in Fig. 4.4 and are discussed
further in Sec. 4.3. Because of the relatively high cost of the material and of
cell fabrication, the development of GaAs-based (and InP-based) cells has been
strongly directed toward concentrator use and space applications. General
issues related to GaAs-based solar cells are discussed in several publications
(Fahrenbruch and Bube, 1983; Fraas, 1985; Bube, 1990, 1993; Boes and Luque,
1993).
4.2. GaAs Fabrication Techniques

Single crystals of GaAs are usually grown by the Bridgman technique, although
the Czochralski method can also be used. A high overpressure of As must be
used in synthesis from the elements because the vapor pressure of As is so
much larger than the vapor pressure of Ga. Common dopants include S, Se,
Te, Sn, Si, C, and Ge as shallow donors, and Zn, Be, Mg, Cd, Si, Ge , and C
as shallow acceptors. The dopants from column IV - C, Si, Ge and Sn - are
amphoteric in GaAs, behaving as donors or acceptors depending on whether
they go onto the Ga or As sublattice, and their electrical behavior depends on
the conditions of growth.
GaAs-based solar cells involve layered structures that are deposited by
liquid phase epitaxy (LPE), chemical vapor deposition (CVD), metallorganic
chemical vapor deposition (MOCVD), or molecular beam epitaxy (MBE). Ba-
sic fabrication details are described in Fahrenbruch and Bube (1983).
A review of LPE is given by Dawson (1972). In the case of GaAs-based
materials, LPE depends on the solubility of As in liquid Ga and AlGa alloys and
the subsequent precipitation of Al,Gal-,As layers onto crystalline substrates,
which determine the crystallographic orientation of the layers. LPE growth
occurs in an atmosphere of high-purity Hz in a growth apparatus fabricated
from high-purity carbon and quartz. The apparatus consists of two portions,
a top one that slides over a bottom one. For the growth of GaAs, for example,
the top portion containing the Ga melt slides over the bottom, which contains
a GaAs source a t one location and a substrate at another. After the melt has
been saturated at a temperature of about 900°C over the GaAs source, the
slider carries the Ga melt over the substrate and the temperature is lowered
at a rate of 0.1-0.5"C min-'. During deposition, the relatively large volume
of Ga acts as a sink for segregated impurities, and since the growth proceeds
near thermal equilibrium, the resulting epitaxial layers are of very high quality.
Variations to achieve gettering of impurities from the substrate during growth,
an "etchback-regrowth" (ER) method to achieve both gettering and the growth
of a compositionally graded Al,Gal-, layer, and other optimization techniques
have been developed to increase cell efficiency (Woodall and Hovel, 1975, 1977;
Bett et al., 1991; Welter et al., 1991; Habermann et al., 1992).
Probably the most widely used technique in recent years is MOCVD, a
variation of the CVD technique. CVD growth of Al,Gal-,As films proceeds
by synthesis from gaseous Ga and As compounds, e.g. by reaction of GaC13 and
AsH3 on a substrate at 600-800°C (Johnston and Callahan, 1976). MOCVD
uses a pyrolysis reaction of an organometallic Ga compound (such as trimethyl-

gallium) and AsH3 a t an rf-heated substrate (Dupuis et al., 1977; Dapkus et al.,
1978). In this technique growth is done in a cold-wall reactor and material is
deposited only on heated areas. Both processes use Hz as a carrier gas at
atmospheric pressure. MOCVD is currently the growth method of choice for
large scale, commercial production of 111-V solar cells.
Although the large difference in vapor pressures of the elements make
achievement of stoichiometry impossible in standard vacuum evaporation of
GaAs from the compound, physical vapor deposition is possible due to the
ability to dissociate AS^. High quality layers can also be grown by molecular
beam epitaxy (MBE) (Casey and Panish, 1978).
4.3. GaAs-Based Solar Cell Development

The highest efficiencies using any materials (with Si a close second) have been
achieved with solar cells based on GaAs and its solid solutions. GaAs has the
optimum band gap for a single-junction solar cell, a high absorption coefficient,
and the highest theoretical efficiency (about 39% for single-junction cells under
1000 suns). It can also be used in alloy form with other related materials, such
as AlGaAs and InGaAs. A history of GaAs solar cell development is given by
Anspaugh (1996).
In the development of GaAs-based solar cells the p+-AlGaAs/pGaAs/n-
GaAs heteroface junction (or buried homojunction) of Fig. 4.3 plays a dom-
inant role. In this section we summarize some of the main developments in
GaAs solar cells of this type, as well as a few others of interest. For more
details see Fahrenbruch and Bube (1983). In Sec. 4.4 we present a similar
discussion for InP-based solar cells.
Heteroface Single Junction Cells

Except for the early report of a 4% p-n homojunction solar cell (Jenny et al.,
1956), the effective development of GaAs-based solar cells has been consider-
ably more recent. Gobat et al. (1962) reported a p-n junction cell with an effi-
ciency of 11%,and in 1970 Alferov et al. (1971) reported the first pAlGaAs/n-
GaAs heterojunction structure with an AM0 efficiency of 10-11%. In 1972 the
heteroface structure shown in Fig. 4.3 was developed and an efficiency of 15.3%
at AM1 and 19.1% at AM2 was reported with a pAlo,~Gao.sAs/pGaAs/n-
GaAs cell fabricated by LPE (Woodall and Hovel, 1972). The intermediate
p t y p e layer was formed by diffusion of Zn during t,he AlGaAs deposition.
Gallium Arsenide and O t h e r 111-V Materials 117
Subsequently heteroface structure cells were reported with efficiencies of 24.7%

at AM1 ( concentration 18Ox) with a graded AlGaAs layer (Sahai et al., 1978),
21% at AM1.4 without concentration (James and Moon, 1975), and 21.9%
at AM1 without concentration (Woodall and Hovel, 1977). More recently
records for highest solar-cell efficiency were held by the following GaAs-based
solar cells: 22.4% for a thin-film cell, 24.3% for a single junction without
concentration, and 29.2% for a single junction with concentration (Hubbard,
1989; Hubbard and Cook, 1989; Gale et al., 1988, 1989; Vernon et al., 1989).
The general concept of the cell structure shown in Fig. 4.3 has been changed
little in recent years except for variations in thickness and composition of the
layers. Although a large fraction of the carriers photogenerated at the light-
incident surface of the p+-AlGaAs is lost by surface recombination, only a small
fraction of the total light current is generated there because of the large band
gap of the AlGaAs. Good lattice matching and fabrication processes that yield
a clean interface result in AlGaAs/GaAs interface recombination with a n inter-
face recombination velocity less than lo4 cm sec-'. The dark current-voltage
characteristics of GaAs-based solar cells correspond remarkably well to either
the injection model (see Eqs. 1.17 and 1.18) with A = 1, or the recombination
model (see Eqs. 1.19 and 1.20) with A = 2; for high concentration light levels
most cells show A = 1 with correspondingly low values of I,.
Optimization of the cell performance calls for (a) minimization of the width
of the p+-AlGaAs layer consistent with a sufficiently low spreading resistance,
(b) adjustment of the p G a A s layer thickness to maximize current generation
and collection, with a thickness of about 1/4 of the electron diffusion length
(5-8 pm) indicated (Van der Plas et al., 1978), and (c) control of the doping
level in the p G a A s and n-GaAs to obtain a high V,, while retaining long
carrier diffusion lengths.
One of the major advantages of the GaAs-based solar cell is its insensitiv-
ity to an increase in temperature; most measurements indicate a monotonic
decrease in efficiency of 0.033 percentage points per "C, i.e. a decrease from
20.00% to 19.67% for a 10°C rise in temperature (Stuerke, 1978). An assess-
ment of the high temperature stability of GaAs solar cells with high temper-
ature contacts indicated minimal electrical degradation for 5 min at 550°C or
for 15 min at 490°C; by elimination of processing defects and improved surface
passivation, stability up to 600°C should be achievable (Tobin et al., 1988).
As for other solar cells, the efficiency increases with concentration of the
light for AlGaAs/GaAs solar cells. This is shown in Fig. 4.5, which also shows
the effect of series resistance (Sahai et al., 1978). If the series resistance can
-
-
-
-
-
SERIES RESlSTAmE VHUES Wovn IN n cm2
0.w I ~ . . . I . . . . I . . .._
1.00 1o.m loo.w lm.w 1.W4
CONCENlPATIW
Fig. 4.5. Calculated solar efficiency as a function of concentration ratio for an AlGaAs/GaAs
LPE cell for various values of lumped series resistance. (Reprinted with permission from
R. Sahai et al., 13th IEEE Photovoltaic Specialists Conference, p. 946, (1978). Copyright
1978 IEEE, NY.)
be kept to less than l o p 3 ohm-cm2, then concentration ratios of l o 3 and above

are desirable; in one design a p+-GaAs layer is inserted between the contact
metallization and the p+-AlGaAs window to reduce contact resistivity and
an overall value of series resistance was obtained between 4 x and 4 x
ohm-cm’.
Heteroface solar concentrator cells with efficiencies above 27% at solar con-
centrations over 400 suns in both n-p and p-n configurations have been investi-
gated (MacMillan et al., 1988a; Kaminar et al., 1988). The higher efficiencies
were obtained through improved control of the MOCVD growth conditions
and improvements in cell gridline definition and edge passivation. Further
optimization may be capable of increasing the efficiency to about 30% for con-
centrations of 500-1000 suns. A similar technique has been used to produce a
GaAs solar cell with 24.0% efficiency without concentration, corresponding t o
the cell structure shown in Fig. 4.6 (Bertness et al., 1988).
A variation on the procedure for AlGaAs/GaAs solar cells is the deposition
on an inactive Ge substrate (Datum and Billets, 1991). Major advantages
of the use of the Ge substrate include lower wafer cost, fracture toughness
FRONT CONTACT
AR COATING
0.6v CAP
300A D AI,.G~~.AS WINWW
3 . 2 ~n GaAs BASE
O l v n AIozGao& BACKWINWW
0.51” n+ GaAs
SUBSTRATE
t BACK CONTACT I
Fig. 4.6. Solar cell structure for a 24.0% efficient GaAs solar cell. At 1 sun, & = 1.05 V,
Jsc = 27.1 mA/cm2, fill factor = 0.845. (Reprinted with permission from K. A. Bertness
et al., 20th IEEE Photovoltaic Specialists Conference, p. 769 (1988). Copyright 1988 IEEE,
NY .)
twice that of GaAs, and a higher tolerance to reverse current requirements.

This work can be considered as the first step in the development of a poly-
crystalline GaAs solar cell deposited on a polycrystalline Ge substrate with
efficiency comparable to state-of-the-art polycrystalline cells such as CdTe and
CuInSez (Venkatasubramanian et al., 1993, 1995, 1996). Solar cell parameters
for AM1.5 radiation were &, = 0.99 V, J,, = 23.1 mA/cm2, fill factor of 0.79,
and efficiency of 18.2% for a 4 cm2 cell at AM1.5.
Related research concerns the fabrication of GaAs/AlGaAs thin film solar
cells using the epitaxial liftoff (ELO) technique, which allows the transfer of
these cells onto non-absorbing glass substrates (Hageman et al., 1996; Lee
et al., 1996). Also as part of a program to fabricate GaAs cells from film
structures grown on Si substrates coated with a GaP film, the properties of
GaAs solar cells grown on (100) GaP by MOCVD have been investigated, with
the best efficiency to date being 10.2% (Olsen et al., 1996).
A method for the hybrid MBE/LPE growth of GaAs(A1GaAs) layers on
Si substrates has been developed (Bett et al., 1992; Baldus et al., 1994a).
Low-temperature (T < 400°C) LPE from a Sn-based melt, followed at higher
temperatures by LPE from Ga-based melts, were used for the growth of GaAs
(AlGaAs) layers on Si substrates previously covered by MBE epitaxially grown

GaAs, to achieve planar growth without microcracks or dissolution defects.
Bismuth was investigated as an alternative to Ga and Sn solvents for the growth
of GaAs layers by LPE on GaAs (MBE or MOCVD)/Si substrates a t low
temperatures (7’ 5 SOOOC) with Sn as an n-type dopant at these temperatures
(Baldus et al., 1995). Attempts to use Zn p t y p e doping in GaAs grown from
Bi-based melts were not reproducible.
The influence of substrate position (vertical or horizontal) during LPE-ER
processing was investigated (Baldus et al., 199413, 1 9 9 4 ~ ) A
. Zn post-diffusion
for GaAs LPE-ER concentrator solar cells was developed to reduce the contact
resistivity to < lo-* R-cm2 (Blug et al., 1995).
Transient photoluminescence decay, also known as time-resolved photo-
luminescence, has been used for the evaluation of GaAs solar cell materials
and structures (Ahrenkiel et al., 1990; Ehrhardt et al., 1991; Ahrenkiel, 1992;
Ahrenkiel et al., 1993). This is a quick and contactless technique that di-
rectly measures the excess minority-carrier density. High resolution is obtained
P,” = 100 M/d T = 300 O X

WATER FILTERED NO AR COATING
TUNGSTEN LIGHT
0
3.
I
0.1
0.502
I
0.2
9.8
I
0.3
I
0.4
VOLTAGE, V
;;!0.5 0.6
Fig. 4.7. Light current/voltage curves for Au/GaAs Schottky barriers for various treatments
of the GaAs surface before application of the metal barrier contact. No antireflection coating
is present. (1) “Clean” interface, (2) GaAs surface exposed to air at 300 K for 4 hr, (3)
exposed t o air at 300 K for 95 hr, and (4)exposed t o air at 403 K for 70 hr. (Reprinted with
permission from R. J. Stirn and Y. C. M. Yeh, Appl. Phys. Lett. 2 7 , 95 (1975). Copyright
1975 American Institute of Physics.)
through the use of a focused laser beam as the excitation source. Using a
theoretical model to interpret measured photoluminescence decay transients,
minority carrier properties in GaAs solar cells can be determined at different
stages of processing. The measurements also provide minority carrier param-
eters, such as lifetime and interface recombination velocity, useful for device
modeling.
MIS Cells
The performance of Schottky barriers on GaAs can be considerably enhanced
by the inclusion of an interfacial insulator layer between the metal and the
GaAs to form an MIS device. Figure 4.7 shows the striking dependence of
open-circuit voltage in Au/oxide/GaAs MIS junctions on the introduction of
an insulating oxide layer (Stirn and Yeh, 1975, 1977; Stirn et al., 1977). High-
efficiency cells can be made either by water-vapor thermal oxide growth or by
deposition of Sb203 onto suitably etched GaAs surfaces. These were called
AMOS cells (antireflection-coated metal oxide semiconductor) and gave effi-
ciencies up to 17%.
It is the increase in diode factor A caused by the oxide layer that is the
primary contributor t o the increased open-circuit voltage. For AMOS cells on
(100) GaAs surfaces, oxidation causes a n increase in A from 1.0 to 1.2 without
an increase in J,. On (111) GaAs surfaces, on the other hand, J , increases on
oxidation by about an order of magnitude, and diode factors of 1.4 to 1.6 are
found.
An n-i-p structure for a GaInP solar cell with an efficiency of 15.7% un-
der AMO, among the highest efficiencies of GaInP single junction cells, was
achieved by introducing an undoped, intrinsic GaInP layer a t the p n junction
to reduce the interdiffusion of Zn into the emitter, and separating the p and
n-regions (Tsai et al., 1995).
C L E F T Films
GaAs is the only material of current interest for solar cells that can be fabri-
cated in the form of a single-crystal thin film solar cell by a desirable process
(Gale et al., 1988, 1989). This possibility is made economically attractive by
the fact that the film can be grown on a reusable, single-crystal GaAs substrate
by the technique known as “cleavage of lateral epitaxial films for transfer”
(CLEFT). The CLEFT process does away with the necessity of using thick,
non-reusable, expensive GaAs substrates.
The various steps in CLEFT fabrication are as follows (Fraas, 1985): (a)
the single-crystal substrate is coated with carbon before epitaxial layer growth,
(b) narrow slits are left in the carbon where the single crystal is exposed, (c)
epitaxy is nucleated in the slits and the similarly oriented crystallites grow
laterally rapidly across the carbon until they join to form a continuous film,
(d) the thin-film solar-cell layers are then grown, (e) contacts are added and
the film is glued to a glass superstrate, (f) the master substrate is removed by
cleaving and can be reused.
GaAs Alloys
In,Gal-,As concentrator cells have been prepared using MOCVD on GaAs
substrates, with a band gap of 1.15 eV for x = 0.25, and 1.35 eV for x = 0.07
(Werthen et al., 1988). With a possible long range application to multijunc-
tion cells, these single-junction cells showed efficiencies greater than 24% at
400 suns. The cell with x = 0.25 has about the same band gap as Si, but has
a direct band gap, and yields & = 0.80 V compared with 0.67 V for Si. Im-
provements in current collection should lead to considerably higher efficiencies
for the InGaAs cells.
Multijunction or Tandem Cells

Multijunction cells consist of devices involving more than one solar cell in such
a way that the higher-energy solar radiation is absorbed by a larger band-gap
solar cell, and the residual lower-energy solar radiation is absorbed by a smaller
band-gap solar cell. One way to achieve this is to use an optical beam-splitter
that reflects different portions of the solar spectrum to different cells. Such a
beam splitter, for example, was built to separate the solar spectrum into two
portions matching the band gaps of AlGaAs and Si (Borden et al., 1981).
An operationally preferable way to achieve the same goal is to stack two
or more solar cells so that the solar radiation passes through the larger band-
gap material first, and then the residual radiation passes through the smaller
band-gap material. This goal can be achieved in one of two ways: (a) by
mechanically stacking different solar cells (MSMJ), with examples given in
Sec. 4.5, and (b) by fabricating a monolithic multijunction structure using a
process such as MOCVD.
One of the first successful attempts to produce a monolithic tandem solar
cell (sometimes called a “cascade structure”) involved the use of six or seven
layers of GaAs and AlGaAs materials on a GaAs substrate to form a mono-
lithic two-junction structure, internally connected in series by a transparent,
low-resistance p+-nf junction. Test cell efficiencies were about 9% (Bedair

et al., 1978, 1979).
Multijunction cells have been developed using different alloys of GaAs
(Lewis et al., 1988; MacMillan et al., 1988b, 1989; Virshup et al., 1988).
Achievements in this effort include a monolithic, two-terminal, two-junction
AlGaAs/GaAs cell with efficiency of 27.6% without concentration (MacMillan
et al., 1989), a 16.5% three-terminal, two junction 1.72 eV AIGaAs/l.l5 eV
GaInAs multijunction (Lewis e t al., 1988), and a 23.9% monolithically grown,
two junction 1.93 eV/Alo.35Gao.65As/l.42 eV GaAs multijunction cell (Virshup
et al., 1988), which from top metal to back contact includes eleven separately
deposited layers using MOCVD, as shown in Fig. 4.8. A goal of the work was to
produce a monolithic, three-junction device based on AIGaAs/GaAs/InGaAs
grown by MOCVD.
1
0 llpm
4
ni AI.Gq .h
C M R
1
WINDOW
- 1
--___----
0 lSlrm n A10.376.0- ----- EMITTER
UPPER CELL
3Wrm P *lo.nwo- TTOM M E T A L CELL EASE
TOP METAL
OlJum p' AIxGalxh STOP ETCH
O U m P *10.37Gq(LJA* UPPER CELL BOTTOM CONTACT
OlZum n* AI.G.1 .AI STOP ETCH

OUrm n A1037696MI LOWER CELL TOP CONTACT
0 Wum n* Ala9GarAi WINDOW
N N
N
SUBSTRATE-
I
t
350 "rn p Gar
BACKCONTACT
I1
Fig. 4.8. Solar cell structure for a 23.9% efficient monolithically grown, two-junction solar
cell with an A I o . ~ ~ G ~ top. ~ cell s a GaAs bottom cell. At 1 sun, q50c = 2.41 V,
~ A and
Jsc = 14.9 mA/cm2 and fill factor = 0.84. (Reprinted with permission from G. F . Virshup
et al., 20th IEEE Photovoltaic Speczalists Conference, p. 441 (1988). Copyright 1988, IEEE,
NY.)
GaInAsP alloys provide a range of possibilities for use in multijunction solar

cells. Two compositions of GaInAsP have been shown capable of producing
solar cells with an efficiency greater than 21% (Sharps et al., 1993). These
cells were grown in an organometallic vapor phase epitaxy (OMVPE) reactor
at 675°C. Precursors were trimethylgallium, ethyldimethylindium, trimethyla-
luminum, arsine, and phosphine. Diethylzinc was used to supply the p-type
dopant and a 50 ppm H2Se in H2 mixture was used to supply the n-type
dopant. For terrestrial applications G ~ o . ~ ~ I ~ o . ~ ~(band A s ogap
. ~ =~ P ~ .
1.55 eV), grown on p-GaAs, forms a cell with & = 1.047 V, J,, = 22.5 mA/
cm2, fill factor = 0.849, and efficiency = 21.8% for AM1.5 radiation and
23.4% for irradiation by 9.73 suns. Plans are underway to fabricate a mono-
lithic multijunction cell with the Gao.8~Ino.l6Aso,s~Po.~2 cell on top, then a
Gao.84In0.~sAs0.68Po.32 tunnel diode, and a Ge cell on the bottom, on which
r 1
n'GaAs
0.5 p n
- 10'8 ern.'
n++-GalnP - 1019 cm-3
n'GalnAsP Ix 10'8 3.5 pm
n'Gr I x 10'8 (3111.3 1 opm
* I x 10)' 6.0 pm
I we Substrate -300p
Mrlnl
Fig. 4.9. Solar cell structure for a possible Gao.64Ino.16ASo.68Po.3z/Gemonolithic multi-

junction cell, involving a Gao.84Ino.lsAso.68Po.32 tunnel diode. (Reprinted with permission
from P. R. Sharps et al., 23rd IEEE Photovoltaic Specialists Conference, p. 633 (1993).
Copyright 1993 IEEE, NY.)
Si doping spike
n= 6 x 10’’ I
0.025
0.1
AllnP
GalnP
[si 1 n= 4 x 1017
n= 2 x 10’8 I (window)
0.5 GalnP p= 1 . 5 10”

~
(1.86 eW
c I I
I 0.05 GalnP (1.88eV) p = 3 X 1 0 * I I (BSF)

0.011 ~ a ~ ~ sC I ~ = ~ X ~ O ~ ~
I I I
substrate GaAs Zn-doped
thickness (pm) doping ( ~ m - ~ )
Fig. 4.10. Solar cell structure for AM0 standard solar spectrum for a GaInP/GaAs monc-
lithic multijunction. (Reprinted with permission from K. A. Bertness et al., 24th IEEE
the G a o . ~ 4 I n o . ~ 6 A s o . ~ ~can
P 0 . 3be
~ grown directly without the buffer layer
normally needed t o avoid the propagation of defects from the substrate. A
schematic of this proposed cell is given in Fig. 4.9. For space applications
Gao.6sIno.32ASo.34Po.66(band gap = 1.7 e v ) has demonstrated good radiation
resistance, with &c = 1.161 V, J,, = 28.9 mA/cm2, fill factor = 0.86 and
efficiency = 21.4% for AM0 illumination.
Record-breaking efficiencies have been reported for GaInP/GaAs two-
terminal multijunction cells: 29.5% for one-sun AM1.5, 30.2% for 160-suns
AM1.5, 25.7% for one-sun AMO, and 19.6% at AM0 after cm-’ 1-MeV
electron irradiation (Bertness et al., 1994). Efficiency advances were attained
concentration (suns)
Fig. 4.11. Efficiency of a GaInP/GaAs multijunction under AM1.5 radiation as a function

of the concentration. (Reprinted with permission from K. A. Bertness e t al., 24th ZEEE
primarily by improving interface passivation layers in the cells and by reducing

grid coverage. The solar cell structure for a GaInP/GaAs multijunction cell is
shown in Fig. 4.10, and the dependence of efficiency on solar concentration is
given in Fig. 4.11.
A 25.8% efficient mechanical stack GaAs/Si concentrator tandem-solar cell
has been fabricated using an LPE-grown GaAs top-cell (Blieske e t al., 1994).
4.4. InP-Based Solar Cells
InP, like GaAs, is a direct band-gap material with a band gap of 1.34 eV, close
to the maximum for solar energy conversion. Also like GaAs, homojunction
cells are limited by surface recombination at the incident surface (Galavanov
et al., 1967), but heterojunctions with good lattice matching, and heteroface
junctions (buried homojunctions), are much more efficient. InP crystals are
grown by the Czochralski method at high pressures or by using a liquid encap-
sulation technique to preserve stoichiometry.
Heterojunction Cells
Highly efficient CdS/InP heterojunction cells have been fabricated by vac-
uum evaporation, chemical vapor deposition, and close-spaced vapor transport
(CSVT). For more details see Fahrenbruch and Bube (1983).
Gallium Arsenade and Other III-V Materials 127
AEc = 0.112 eV
6P = 0.088 eV
InP
2.42 eV = 6.1 10” cn-3
v 4
n - CdS
2.8 x 1019 cme3
Fig. 4.12. Energy band diagram for a CdS/InP heterojunction prepared by close-spaced
vapor transport of a CdS film onto single crystal InP. (Reprinted from A. Yoshikawa and
Y. Sakai, Solid State Electronics 20, 133 (1977). Copyright 1977, with kind permission from
Elsevier Science Ltd., The Boulevard, Langford Lane, Kidlington OX5 lGB, UK.)
An efficiency of 12.5% for a n n-CdSlpInP heterojunction was reported by

Wagner et al. (1975) for which the CdS layer was formed by vacuum deposition
on InP single crystals doped with Cd. A schematic energy band diagram is
given in Fig. 4.12. CdS is a n excellent choice for such a heterojunction since
there is only a 0.32% lattice mismatch between the (111) plane of zincblende
InP and the basal plane of wurtzite CdS. Also the tetrahedral atomic distance
is 25.33 nm in InP and 25.32 nm in CdS.
Heteroface Cells
A heat treatment a t about 600°C in a non-oxidizing atmosphere improves the
CdS/InP cell described above, giving an efficiency of 14% (Shay et al., 1976),
and suggesting the formation of a heteroface junction, n-CdS/n-InPlpInP.
The efficiency of a CdS/InP cell was further increased t o 15% by using
chemical vapor deposition of CdS on InP using an open-tube H2S/H2 flow
system (Shay et al., 1977; Bettini et al., 1977, 1978). Once again the properties
of the cell suggest that it is an InP buried homojunction. Solar cell parameters
for AM2 illumination were = 0.79 V, Jsc = 18.7 mA/cm2, f f = 0.735.
In view of the importance of lattice matching for high efficiency that un-
derlay the above discussion of CdS/InP solar cells, it is perhaps surprising to
InP
ITO
20 In‘ 16 17
nf- 1x10 n-1x10 p-3x10
Fig. 4.13. Energy band diagram for a n n - I T O / n - I n P l p I n P buried homojunction produced

by rf sputtering of the I T 0 onto p I n P . (Reprinted with permission from M. J. Tsai e t al.,
J . A p p l . Phys. 51,2696 (1980). Copyright 1980 American Institute of Physics.)
find that cells with efficiency greater than 14% can be made from junctions
between indium-tin-oxide (ITO) and p t y p e InP for which the lattice mismatch
is large (Sree Harsha et al., 1977). Subsequent investigation (Bachmann et al.,
1979; Tsai et al., 1980) has shown that the high efficiency of the ITO/InP
junctions is the result of the formation of a buried homojunction in the InP
by the action of sputter deposition, with the resulting band diagram shown in
Fig. 4.13.
Epitaxial Film Cells

Single-crystal p t y p e InP homoepitaxial layers were grown by a chemical va-
por deposition method on single crystal p+-InP substrates (Manasevit 1978).
CdS/InP junction cells made by vacuum evaporation of CdS onto these lay-
ers showed efficiencies between 8 and 12%. Similar results were reported for
sputtered IT0 layers on homoepitaxial p I n P layers.
The electrical properties were determined (Tsai and Bube, 1978) for a series
of epitaxial n-type undoped InP films deposited on high-resistivity GaAs:Cr or
1nP:Fe substrates by MOCVD, which showed that epitaxial undoped n-type
Gallium Arsenide and Other III- V Materials 129
InP films can be deposited by MOCVD on I n P substrates to produce material

with mobility close to that of single crystal InP. The same is true for GaAs
substrates only for values of electron densities greater than 10l6 ~ m - ~ .
Homojunction Cells
A large scale commercial process has been described for the fabrication of n + p
homojunction InP solar cells for space power generation, involving the diffusion
of sulfur into p t y p e InP substrates in a sealed quartz ampoule (Okazaki et al.,
1988). The best 2 x 2 cm2 cell had q5,, = 0.828 V, J,, = 33.7 mA/cm2, fill
factor = 0.816 and efficiency = 16.6% for AMO.
In spite of the front surface recombination problems, and in the absence
of a suitable lattice-matched, wide-bandgap material that could be used as a
window layer for passivation of the front surface, a high efficiency n f p junction
has been prepared by MOCVD with a graded-junction, or front-surface-field
structure, to decrease front surface recombination losses (Keavny et al., 1990).
The cell consists of a p t y p e heavily-doped buffer layer, a lightly-doped p
type base layer, an n-type emitter, and an n-type Ino.53Gao.47As cap layer.
The n-type emitter is made up of two layers: A moderately heavily doped
region (3 x 10'' ~ m - near ~ ) the junction, and a very heavily doped region
(3 x lo" cmP3) at the surface. After metallization with Cr-Au-Ag, the cells
were mesa etched, and the InGaAs layer was removed from the active area
with a selective etch. Finally the cells had a ZnS/MgF2 two-layer antireflection
coating. A 4 cm2 cell for AM0 had & = 0.876 V, J,, = 36.34 mA/cm2, fill
factor = 0.824 and efficiency = 19.1%. The cells showed a degradation of 4.7%
after exposure to 1014 cmP2 1 MeV electrons.
Hydrogenation of n+-p InP solar cells has been shown to increase the effi-
ciency from 14.8% to 17.5% a t AM0 because of a reduction in carrier concen-
tration in the near-surface layer due to the formation of an acceptor-hydrogen
complex (Min et al., 1993).
MIS Cells
MIS cells with efficiency of 14.5% have been fabricated on InP, similar to those
described above for GaAs (Kamimura et al., 1981).
Polycrystalline InP Cells

Because of the expense of InP, it has been attempted to use thin films of
polycrystalline InP less than 2 pm thick with grain size about the same as
-
E InP/CdS SOLAR C E L L S
(b) FORWARD VOLTAGE ( V )
Fig. 4.14. Comparisons of CdS/InP photovoltaic junction properties for single-crystal I n P

and polycrystalline InP cells. (a) Wavelength dependence of the quantum efficiency. (b)
Forward-bias current/voltage curves. (Reprinted with permission from J. L. Shay et al.,
IEEE Tmnsactions Electron Devices ED-24, 483 (1977). Copyright 1977, IEEE, NY.)
the thickness. CdS/InP junctions have been prepared on polycrystalline I n P

deposited by PC13 CVD on carbon substrates (Bachmann et al., 1976; Shay
et al., 1977). Values of Jsc are high, but so are values of J , because of the
polycrystalline nature of the material, and doc is considerably reduced; the
highest efficiency values were 5.7%.
Gallium Arsenide and Other 111-V Materials 131
Figure 4.14 compares the properties of CdS/InP cells prepared on single-

crystal InP with those prepared on polycrystalline InP (Shay et d., 1977). The
quantum efficiency of the polycrystalline I n P cells is only slightly less than that
of the single-crystal cells, but the junction characteristics show both a hundred
fold increase in J , and a decrease in A from 2.0 to 1.7, resulting in a decrease
in & to values of about 0.46 V.
4.5. Hybrid Multijunction Solar Cells
A number of multijunction combinations have been investigated, using a GaAs-

based solar cell as one member.
G aA s / S i
A record-breaking 31% efficient GaAs/Si mechanically stacked multijunction
(MSMJ) concentrator solar cell has been developed (Gee and Virshup, 1988).
Special care was needed to insure that the GaAs cell had maximum trans-
parency for sub-band gap radiation. InGaAs is a possible substitute for the Si
cell.
GaAs/CuInSez
An MSMJ four-terminal device, consisting of a GaAs thin film top cell made by
the CLEFT process and a ZnCdS/CuInSez thin bottom cell, gave an efficiency
of 21.3% (19.5% from the GaAs cell, and 2.8% from the CuInSe2 cell) (Stanbery
et al., 1987; Kim et al., 1988). Good radiation resistance makes these cells
candidates for flat-plate space applications.
GaInPz/GaAs
Efficiencies of about 25% have been reported for monolithic GaInPz/GaAs
multijunction cells with a tunnel-junction interconnect (Olson et al., 1989;
Kurtz et al., 1990), and plans for a GaInPz/GaAs/Ge triple junction have
been described (Chiang et al., 1994). Comparable efficiencies are obtained for
p-on-n GaInPz/GaAs two-terminal, monolithic multijunction cells (Sharps
et al., 1994).
A single junction InGaP solar cell with an n-ppf structure and a BSF
achieved an efficiency of 18.48%, and InGaP/GaAs monolithic multijunctions
were prepared with an efficiency of 27.3% (Takamoto et al., 1994; Kurita et al.,
1995).
GaAs/GaSb
An efficiency of 34% has been achieved in an MSMJ GaAs/GaSb cell (Fraas
et al., 1990, 1991). Cells based on pn-InGaSbAsln-GaSb lattice matched
heterostructures have also been fabricated by LPE with the long-wavelength
edge of photosensitivity of the cells at about 2.15-2.2 pm (Andreev et al.,
1996).
InP/GaInAs
An efficiency of 22.2% has been achieved with a monolithic multijunction con-
centrator cell based on InP/GaInAs, and research has been carried out on
other variations in this system (Wanlass et al., 1991, 1994).
4.6. Radiation Resistance

Since 111-V solar cells have considerably better radiation resistance than Si
solar cells (the shorter intrinsic carrier lifetime in 111-V materials due to the
direct band gap makes it less sensitive to the creation of imperfection recom-
bination centers), they are especially favored for space applications where the
power-to-weight ratio and the resistance t o radiation damage are of prime
importance. InP-based cells show better radiation damage resistance than
GaAs-based cells. A review of GaAs solar cell properties with special reference
to radiation effects is given by Anspaugh (1996).
Fabrication procedures can also be varied to increase resistance to radiation
damage. One such procedure involves band-gap grading via compositional
grading to achieve high electric fields near the incident surface to reflect carriers
away from the surface and reduce surface recombination loss, or to achieve
high electric fields throughout the generation region to increase the effective
diffusion length there (Tauc, 1957; Hutchby and Fudurich, 1976; Woodall and
Hovel, 1977; Kordos et al., 1979; Kordos and Pearson, 1980).
The influence of 20.6 MeV proton and 1 MeV electron radiation on CdS/InP
solar cells has been investigated (Botnaryuk et al., 1990). It was found that
CdS/InP solar cells possess a higher resistance to radiation than either Si or
AlGaAs/GaAs cells. Since indium is an expensive metal with a rather small
natural abundance, InP cannot compete economically in most applications
with GaAs and other solar cells, but since it does have a better radiation
tolerance than GaAs, development for such applications continues (Gessert
et al., 1989).
Radiation effects due to protons and electrons have been investigated with
n f - p homojunction InP solar cells made by closed-ampoule diffusion of In2S3
Gallium Arsenide and O t h e r 111-V Materials 133
into a p t y p e substrate (Takamoto et al., 1990). The greatest damage is done

by low-energy protons stopped in the active region. A 50 pm coverglass shields
the cell from low-energy protons, which is effective because InP solar cells are
highly resistant to electron and high-energy proton irradiation. Analysis of
space flight data on InP solar cells indicates that InP cells are suitable for
space applications (Takahashi et al., 1991; Yamaguchi et al., 1990, 1991), and
that the development of thin film InP cells is highly desirable.
x 10-8
0 0.2 0.4 0.6 0.8

InP Composition
Fig. 4.15. Changes in damage constant K L for minority-carrier diffusion length for InP-
related materials and GaAs as a function of InP composition. (Reprinted with permission
from M. Yamaguchi et al., Japanese J. Appl. Phys. 34, 6222 (1995). Copyright 1995,
Japanese Journal of Applied Physics.)
The radiation resistance of a number of different compound semiconduc-

tor solar cells to 1 MeV electrons has been recently investigated (Yamaguchi,
1995), including InP, InGaP, InGaAsP, GaAs, AlGaAs, InGaAs, Si, Ge, and
CuInSez. The major conclusions of the study are: (a) I n P and CuInSea have
the highest radiation resistance; (b) differences of radiation resistance between
GaAs-based solar cells such as GaAs, AlGaAs, and InGaAs are due to band-
gap energy effects with the resistance to damage increasing with band gap; (c)
the superior radiation resistance of CuInSe2 cells is associated with the higher
optical absorption coefficient of CuInSe2 compared to other materials; and (d)
the better radiation resistance of InP-based solar cells, such as InP, InGaP,
and InGaAsP, is due to a lower defect introduction rate compared to other

materials. Figure 4.15 shows the dependence of the damage constant K L for
InGaAsP alloys as a function of the composition (Yamaguchi et al., 1995). K I ,
is defined by K L F = (l/L$) - (l/L;), where F is the integrated fluence, LF
is the minority-carrier diffusion length after irradiation, and Lo is the minority
carrier diffusion length before irradiation. The value of K L decreases linearly
with the fractional InP composition of the materials.
CHAPTER 5
CADMIUM TELLURIDE AND OTHER

11-VI MATERIALS
5.1. Overview
When work on thin-film Cu,S/CdS cells came t o a n end because of the un-
avoidable degradation associated with the effects of Cu diffusion, the question
naturally arose as to what other p t y p e materials could form useful hetero-
junctions with CdS. Two such materials are InP, discussed in Chapter 4,and
CuInSe2 discussed in Chapter 6. It would also be desirable to find suitable
p t y p e materials among other 11-VI compounds, capable of being deposited in
thin film polycrystalline form in ways analogous to those used for CdS. Of the
six 11-VI chalcogenides (ZnS, ZnSe, ZnTe, CdS, CdSe, and CdTe) only ZnSe
and CdTe can be prepared in both n-type and p t y p e form, and of the rest only
ZnTe can be prepared in high-conductivity p t y p e form. For the preparation
of p-n heterojunctions from 11-VI chalcogenides, therefore, the choice of the
p t y p e member is essentially restricted to ZnTe or CdTe, since p t y p e ZnSe has
yet to be demonstrated in polycrystalline form. This leaves the nine potential
possibilities summarized in Table 5.1, together with their alloys (Bube, 1976).
The 11-VI compounds n-type CdS and n-type ZnO have been used for the
high-conductivity window-layer in several heterojunction cells and examples
are given in several places in this book.
The two most likely candidates for efficient solar cells are n-ZnCdSlpCdTe
and n-ZnSSelpCdTe. A plot of band gap versus lattice constant for the II-
VI chalcogenides and a few other materials of interest are shown in Fig. 5.1
(Bube and Mitchell, 1993). All of the 11-VI heterojunctions show appreciable
lattice mismatch except n-CdSelpZnTe, but such mismatch by itself does not
appear to be a serious problem for CdTe-based cells. The stoichiometry limits
of existence are shown in Fig. 5.1, although several of the compounds have
been prepared outside these limits in metastable form.
In all of the different ways in which solar cells have been fabricated based
on junctions involving p C d T e crystals and polycrystalline thin films, three
problems appear to be dominant: recombination losses associated with the
135
Table 5.1. Energy Relations at 11-VI Binary Heterojunction Interfaces
Larger Band gap Smaller Band gap Diffusion Lattice

Material ( E c , eV) Material ( E G , eV) Voltage, 4: Mismatch %
n-CdSe (1.70) p C d T e (1.44) 0.57 6.3

p Z n T e (2.26) n-CdSe (1.70) 0.61 0.5
n-CdS (2.42) p C d T e (1.44) 1.02 9.7
n-CdS (2.42) p Z n T e (2.26) 1.06 3.9
p Z n T e (2.26) n-CdTe (1.44) 1.28 5.8
n-ZnSe (2.69) pCdTe (1.44) 1.43 12.5
n-ZnSe (2.69) pZnTe (2.26) 1.47 7.1
n-ZnS (3.70) pCdTe (1.44) 1.62 15.3
n-ZnS (3.70) pZnTe (2.26) 1.66 10.5
a Based on values of electron affinity given in A. G. Milnes and D. L. Feucht (1992)
5.0 5.5 6.0 6.5 7.0

Lattice constant (A)
Fig. 5.1. Band gap versus lattice constant. For hexagonal structures, c ~ * ( 2 ) ’ /is~ used. Only
ternary tie lines are shown. “Estimate” indicates that a linear estimate was used in lieu of
lacking data. (Data compiled by A. L. Fahrenbruch, 1993. Reprinted with permission from
R. H. Bube and K. W. Mitchell, J . Electronic Materials 22, 17 (1993), a publication of the
Minerals, Metals & Materials Society, Warrendale, Pennsylvania 15086.)
Cadmium Telluride and Other 11-VI Materials 137
junction interface, difficulty in doping the p C d T e , and difficulty in obtaining

low-resistance contacts to the p C d T e . These major areas and related topics
are discussed in this chapter.
By 1976 efficiencies between 6 and 7% had been found for (a) evaporated
n-CdS on single crystal p C d T e with or without an indium-tin oxide (ITO)
transparent, conducting coating on the CdS, and (b) a solution-sprayed n-CdS
layer on single crystal p-CdTe (Bube, 1976). Since then a rather wide variety
of film deposition techniques have been used in the fabrication of CdTe-based
solar cells, both in the deposition of window materials on p t y p e single crystal
or polycrystalline CdTe, and in the deposition of polycrystalline p-CdTe layers
themselves. These include vacuum evaporation (VE), hot-wall vacuum evap-
oration (HWVE), close-spaced vapor transport (CSVT) - sometimes called
close-spaced sublimation (CSS), electron-beam evaporation (EBE), chemical
vapor deposition (CVD) or metalorganic chemical vapor deposition (MOCVD),
screen printing (ScP), electrodeposition (ED), spray pyrolysis (SP), and sput-
tering (ST). These techniques are described in this chapter as related to the
development of CdTe polycrystalline thin films for solar cells. A summary of
the general properties of CdTe is available in Zanio (1978).
Attention must also be paid to the potential health and safety issues that
arise because of the toxic nature of cadmium, both in connection with the
manufacturing of CdTe devices, and also during field use (Moskowitz et al.,
1990; Moskowitz and Zweibel, 1990; Moskowitz, 1994). Given the environ-
mental concerns, the development of responsible means for disposing of CdTe
solar cells is essential. The technology is straight-forward (Doty and Meyers,
1988; Patterson et al., 1994) and new science is not required (Birkmire and
Meyers, 1994). Techniques for dealing with off-specification modules and pro-
cess by-products, using acid leaching of the CdTe from the glass substrates
and recovery by means of an ion exchange process, have also been discussed
(Sasala et al., 1994).
A summary of representative solar cell results are given in Table 5.2 (Bube,
1988), showing that CdTe solar cells with an efficiency approaching 10% or
higher have been made as heterojunctions, homojunctions, buried homojunc-
tions and MIS junctions, using single crystal CdTe or thin film polycrystalline
CdTe, and a variety of deposition techniques. A plot of optimum CdTe-based
solar cell efficiencies as a function of year is given in Fig. 5 . 2 , where compara-
ble values for the major competing CuInSe2-based polycrystalline solar cells,
described in Chapter 6, are also included.
Unk.of So. Florida

15 -
8 13-
E -
0 CulnSe,
CdTe
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
5
1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 199
Calendar year a m w
Fig. 5.2. Best one-of-a-kind laboratory cell efficiencies for polycrystalline thin-film cells
based on CdTe or CuInSez. (Reprinted with permission from K. Zweibel et al., 25th ZEEE
Table 5.2. Representative High Efficiency CdTe Solar Cells
Cell Open-Circuit Short-circuit Solar Reference

Voltage, doc Current, J,, Efficiency,
mA/cm2 %
n-CdSlpCdTe 0.84 25.1 15.8 Ferekides et al., 1993
heteroj unction
CdTe by CSVT,
CdS by CBD
(all thin-film cell)
Auln-CdTe 0.81 21.6 15.1 Raychaudhuri et al.,

Schottky barrier 1987
SX n-CdTe
n-CdSlpCdTe 0.82 25.4 15.05 Nishio et al., 1996

heterojunction
CdTe by CSVT
CdS by CVD
C a d m i u m Telluride and O t h e r II-VI Materials 139
Table 5.2. (Continued )

Voltage, & Current, Js, Efficiency,
mA/cm2 %
n-CdSlpCdTe 0.85 21.7 14.2 Ferekides et al., 1996
heterojunction
both layers by
CSVT
n-ITOlpCdTe buried 0.89 20 13.4 Nakazawa et al., 1987

homojunction
I T 0 react. dep. on
SX p C d T e
n-CdSlpCdTe buried 0.75 22 12.8 Uda et al., 1982
homojunction Nakayama et al., 1980
both layers by screen Suyama et al., 1987
printing Matsumoto et al.,
(all thin-film cell) 1984
n-CdSlpCdTe buried 0.67 20 11.7 Yamaguchi el al.,

homojunction 1976, 1977
CdS by CVD on
SX p C d T e
n-CdSlpCdTe 0.76 22.0 11.0 Kim et al., 1994
heterojunction
both layers by
electrodeposition
CdTe homojunction 0.82 21 10.7 Mimila-Arroyo et al.,

p C d T e by CSVT 1979
on large-grain n-CdTe Barbe et al., 1982
n-CdS/pCdo.gHgo.lTe 0.62 27 10.6 Basol et al., 1986

heterojunction
both layers by
electrodeposition
Table 5.2. (Continued )

Voltage, & Current, J,, Efficiency,
mA/cm2 %
n-ITO/pCdTe 0.81 20 10.5 Werthen et al.. 1983b
heterojunction
e-beam evap. I T 0 on
SX p C d T e
n-CdSlpCdTe 0.75 17 10.5 Tyan et al., 1982
heterojunction
both layers by CSVT
n-CdSlpCdTe 0.75 22 10.5 Chu et al., 1987
heterojunction
pCdTe by CSVT
on vac. evap. n-CdS
n-CdSlpCdTe 0.74 22 10.4 Meyers, 1987
hetero j unct ion
pCdTe electrodep.
on S P n-CdS
n-CdSICdTelpZnTe 0.69 22 9.4 Meyers, 1987
n-i-p cell
SP CdS, electrodep.
CdTe, vac. evap. ZnTe
n-ZnOlpCdTe 0.54 19.5 8.8 Aranovich, 1980
heterojunction
n-ZnO by SP on
SX p C d T e
Auln-CdTe MIS cell 0.72 19 8.7 Fulop et al., 1982
by electrodep.
n-ITOlpCdTe buried 0.82 14.5 8.0 Courreges et al., 1980
homojunction
n-IT0 sputtered on
SX pCdTe
C a d m i u m Telluride and Other II-VI Materials 141
5.2. Surface and Contact Properties

Surface Properties
The effects of CdTe surface preparation on the subsequent properties of Cr/
CdTe junctions, and of ITO/CdTe and CdS/CdTe heterojunction solar cells
have been extensively investigated with single-crystal p t y p e CdTe (Patterson
and Williams, 1978; Werthen et al., 1983d).
In a study of cleaved, oxidized, etched and heat-treated p t y p e CdTe sur-
faces, the chemical compounds present on the surface of CdTe have been in-
vestigated by x-ray photoelectron spectroscopy (XPS) after different surface
preparations and correlated with the properties of junctions formed by Cr on
CdTe (Haering et al., 1983).
(7)CLEAVED
I I
CdTe Cd Te02 CdTe Te Te02
Fig. 5.3. Flowchart summarizing the various CdTe surface treatments and their effects.
(Reprinted with permission from J.-P. Haering et al., J . V a c u u m Science and Technology
A l , 1469 (1983). Copyright 1983, American Institute of Physics.)
A flowchart summarizing the various CdTe surface treatments and their

effects is given in Fig. 5.3. Results can be summarized as follows: (1) cleaving
in nitrogen gives a stoichiometric CdTe surface, (2) a 2% Bra-in-methanol
etch (Br:MeOH), or a chromate etch with K2Cr207:HzS04 (Chr) of (110)
or (111) CdTe surfaces results in excess Te, (3) hydrogen heat treatment of
Br:MeOH-etched surfaces results in stoichiometric surfaces by removing excess
Te, (4) oxidation of the (110) CdTe surfaces is much more rapid than the
(111) surfaces, (5) the presence of Te on the Br:MeOH etched surfaces results
in larger J , and reduced &, (6) stoichiometric surfaces obtained either by
cleaving or by hydrogen heat treatment result in junctions characterized by
barrier heights of 0.99 V, and (7) q$c, = 0.5 V is obtainable with Cr/CdTe
junctions formed on stoichiometric CdTe surfaces. Figure 5.4(a) shows the
10-2 c
ld7
10.e
t, 01 02 03 04 05 06
FORWARD BIAS ( V )
(a)
I J(mAlcm2) f
(b)
Fig. 5.4. (a) Dark J-V characteristics of Cr/CdTe junctions formed on (110) surfaces:
cleaved (C), Br:MeOH-etched (E), and Br:MeOH-etched plus hydrogen heat treated (EH).
(b) Light J-V characteristics of Cr/CdTe junctions formed on (110) surfaces: cleaved (C),
Br:MeOH-etched (E), and Br:MeOH-etched plus hydrogen heat treated (EH). (Reprinted
with permission from J.-P. Haering et al., J. Vacuum Science and Technology A l , 1469
dark current-voltage characteristics of Cr/CdTe junctions formed on { 110)

surfaces, and Fig. 5.4(b) shows the light current-voltage characteristics for the
same junctions. Silberman et al. (1983) showed that CdTe cleaved in vacuum
does not oxidize on exposure to dry oxygen unless light or electrons are present.
Surface photovoltage measurements of Br:MeOH-etched single-crystal sur-
faces indicated that the Fermi level was pinned due to the presence of the
etch-induced excess Te layer (Werthen et al., 1 9 8 3 ~ ) .Metal/CdTe junctions
formed on such surfaces show low barriers and no dependence on metal work
function. Stoichiometric surfaces obtained either by cleaving or by hydrogen
heat treatment after etching result in metal/CdTe junctions characterized by
large barriers that depend on metal work function. The dependence of light
current-voltage curves on Cr/CdTe junctions on etching, heat treatment after
etching, and crystal orientation is illustrated in Fig. 5.5.
Fig. 5.5. Light J-V characteristics of Cr/CdTe junctions formed on polished and Br:MeOH
etChed (PE), and polished, Br:MeOH etched and heat treated (PEH) surfaces of different
orientations. (Reprinted with permission from J. G. Werthen et al., J . Appl. Phys. 54,
5982 (1983). Copyright 1983 American Institute of Physics.)
These surface properties were investigated further through the characteriza-

tion of ITO/CdTe and CdS/CdTe heterojunction solar cells formed by electron-
beam evaporation (EBE) of IT0 and CdS onto single crystalpCdTe (Werthen
et al., 1983b). ITO/CdTe cells prepared on polished and Br:MeOH etched sur-
faces showed solar efficiencies of about lo%, with major losses attributable to
reduced fill factors and &,c because of the non-ideal nature of the interface.
ITO/CdTe junctions prepared on cleaved as well as heat-treated surfaces show

poor 4ocbecause of large J , values induced by a necessary air-heat treatment
for I T 0 transparency. CdS/CdTe heterojunctions also show a strong depen-
dence on CdTe surface condition, but with less influence by the junction for-
mation process, with solar efficiencies of 7.5% being achieved on a Br:MeOH
etched and heat-treated surface. Consistent with the results obtained from
metal/CdTe junctions, polished and Br:MeOH etched surfaces result in poor
4,, values, whereas cleaved, as well as polished, Br:MeOH etched, and heat-
treated surfaces result in larger 4ocvalues. It was found that q50c increased
with decreasing hole density in the CdTe, and values of 4,, as high as 0.81 V
were observed for a junction prepared on CdTe with p = 1 x 1015 cmP3, to-
gether with J,, = 19 mA/cm2 and a fill factor of 0.55, to give an efficiency of
10.5%, with no anti-reflection coating.
Heat treatment of p t y p e CdTe:P single crystals in hydrogen at temper-
atures between 310°C and 475°C decreases the hole density near the CdTe
surface by as much as a factor of 25, apparently due to the out-diffusion of
acceptors, and produces an approximately exponential acceptor density profile
(Nishimura and Bube, 1985).
Surface Oxidation
A high-resolution electron microscopy study of a CdTe single crystal, after
being stored in air at room temperature under room illumination for a period
of abut 30 days, showed the existence of a 60 nm thick TeOz layer on the (110)
surface (Ponce et al., 1981).
The effect of this surface oxide layer on the properties of Cr/CdTe junctions
formed on cleaved surfaces exposed to air for different lengths of time was
observed (Werthen et al., 1983a). An increase in open-circuit voltage observed
with length of time the cleaved surface was exposed to air was attributed to
the presence of the TeOz on the air-exposed surface.
Thermal oxidation df single-crystal p t y p e CdTe was carried out in dry and
wet oxygen at temperatures between 350°C and 500°C (Wang et al., 1987).
The growth rate was increased by about a factor of 2 by changing from dry
to wet oxygen, and was slightly higher on (111) Cd and (111) Te faces than
on (110) faces. The thickness of the oxide varied as the square-root of the oxi-
dation time, implying a diffusion controlled process with an activation energy
of 1.2 eV for thermal oxidation. Examination of the oxide by Auger electron
spectroscopy, x-ray photoelectron spectroscopy, and transmission electron mi-
croscopy showed that the composition of thick layers is CdTe03. A related
Cadmium Telluride and Other II-VI Materials 145
study of the solid-state quaternary phase equilibirum diagram for the Hg-Cd-
Te-0 system, including ternary diagrams for Cd-Te-0 and Hg-Te-0, indicated
that CdTeOs is the first oxide to form and remains stable (Rhiger and Kvaas,
1983).
Cr/CdTe and Cr/CdTe03/CdTe (MIS) junctions, involving the thermal
oxide CdTe03, were fabricated on both p and n-type CdTe single crystals
by oxidation of single crystal CdTe after polishing, Br:MeOH etching, and
hydrogen heat treatment (Wang et al., 1989). For n-type CdTe the oxide
increases the open-circuit voltage (to 0.71 V for a 1 nm thick oxide layer)
over that of the Schottky barrier (0.39 V), whereas for p t y p e CdTe the oxide
decreases the open-circuit voltage (from 0.47 to 0.42 V). Postulated energy-
band diagrams for the two types of junction are given in Fig. 5.6(a) for the
Cr CdTeO, p-CdTe
-
Evx
1.3
4.3
f
O.' f f
3 .O
3.2
<
t
-Ec
f 0.5
I
f
(4
Fig. 5.6. (a) Energy band diagram for a Cr MIS Junction on p C d T e crystal with native
CdTeO3 oxide as the insulator. (b) Energy band diagram for a Au MIS junction on n-CdTe
with native CdTe03 oxide as the insulator. (Reprinted with permission from F. F. Wang
et al., J . A p p l . Phys. 6 5 , 3552 (1989). Copyright 1989 American Institute of Physics.)
Au cdTeO3 n-CdTe
(b)
pCdTe and 5.6(b) for the n-CdTe. In p C d T e photogenerated electrons are

partially blocked at the CdTe03/pCdTe interface, become trapped to decrease
the positive charge in the oxide, and decrease the barrier height. In n-CdTe the
oxide is transparent to photogenerated holes, and larger values of open-circuit
voltage than for an MS junction are obtained because majority electrons must
tunnel through the oxide.
Contacts
The work function of p t y p e CdTe is sufficiently large (of the order of 5.7 eV)
that no metal has a large enough work function to make an ideal ohmic con-
tact. In addition, the Fermi energy at the surface can be partially pinned by
surface states, depending on the surface treatment. The effort to obtain a
low-resistance contact with ohmic behavior has therefore focused on obtain-
ing a contact to highly-surface-doped p C d T e suitable for tunneling transport.
Low-resistance contacts to p C d T e have been reviewed by Ponpon (1985) and
Fahrenbruch (1987).
Early work (Gu et al., 1975; Jager and Seipp, 1981) indicated that etching
the surface with K2Cr207:HzS04 provided the basis for a low-resistance con-
tact using Au or Ni-Au. Related results were obtained by Anthony et al. (1982)
who found that the best contact was a CuAu alloy, prepared by co-evaporating
Cu and Au from the same boat with Cu comprising approximately 12 at.%
of the evaporant, on a p t y p e CdTe surface etched with K2Cr207:HzS04 (a
CuAu/Chr contact). Auger profiling measurements indicated that there is a
marked enhancement of the Te/Cd ratio over a region of about 48 nm from
the surface. The presence of Cu in the contact increases the effective doping
density in the depletion region. The contact resistivity at room temperature
depends on the CdTe bulk resistivity, as shown in Fig. 5.7, but it increases
rapidly upon cooling, to a value greater than lo6 ohm-cm2 at 125 K. The
CuAu/Chr contacts were found to be essentially stable a t room temperature,
but increased in resistivity by a factor of about four when annealed between
100°C and 200°C. These contacts could be described by a thermally assisted
tunneling model (Padovani and Stratton, 1966).
Contact resistivities comparable to those of CuAu/Chr contacts can also
be obtained by the use of a material like p Z n T e as the contact material to
polycrystalline CdTe in the formation of p i - n junctions as described below
0.3 0.5 1.0 2 4

Ul-cmt
P,,,
Fig. 5.7. Dependence of contact resistivity on bulk resistivity for CuAu/Chr contacts on
pCdTe at room temperature. (Reprinted with permission from T. C. Anthony et al., J .
Electronic Materials, 11,89 (1982), a publication of the Minerals, Metals & Materials Soci-
ety, Warrendale, Pennsylvania 15086.)
(Meyers, 1989; Nouhi et al., 1989), or ofpHgTe as the contact material because
of its larger work function than p C d T e (Chu et al., 1988). Contact resistances
of the order of 0.4-0.8 ohm-cm2 were obtained for deposition of HgTe, either by
direct combination of the elemental vapors in a gas flow system or by CSVT,
onto large-grain polycrystalline CdTe with resistivity of 200-400 ohm-cm. Thin
(< 100 nm) ZnTe:Cu films were deposited by an electrochemical method to
make contact to the polycrystalline CdTe in a CdTe/CdS/ITO solar cell, giving
higher optical transmission than similar vacuum evaporated ZnTe:Cu contacts
and leading to an 8.7% efficient cell (Mondal et al., 1991, 1992). Cells made
with electrodeposited CdTe and ZnTe:Cu vacuum-evaporated contacts t o the
CdTe have been reported with an efficiency of 12.9% (Tang et al., 1996).
Reproducible low-resistance contacts of the order of 0.01 ohm-cm2 at 30 K
and 0.15 ohm-cm2 at 77 K were achieved on Li-diffused single-crystal CdTe,
using n-butyllithium, with Au as the contact metal (Lee and Bube, 1983). Li
doping achieved a p+ surface layer with p = lo1’ cm-3 that made tunneling
currents possible to produce the low contact resistivities observed (from Au to
pf surface), independent of the bulk resistivity or even the bulk conductivity
type. Unfortunately the contact resistivity changes with time, first decreasing
and then later increasing, and with temperature, probably involving diffusion
of Li acceptors away from the surface and loss of Li acceptors by interaction
with lattice defects or by precipitation. Even so, contact resistivities less than
0.03 ohm-cm2 can be achieved at 300 K for periods of several months.
Subsequent research on these contacts showed that values of contact resis-
tivity as low as 2.1 x l o p 3 ohm cm2 at room temperature and 3.7 x lo-’ ohm
cm2 at liquid N2 temperature can be achieved on Li-diffused CdTe with Au
as the contact metal (Lee and Bube, 1985). An MIS tunnel diode model was
proposed to account for the observed current-voltage characteristics of the con-
tacts, in view of a surface analysis that indicated that the crystalline structure
of the CdTe surface had been greatly disturbed and a Te-rich surface layer
produced, and the degradation of the contacts with time is probably caused
both by diffusion of Li and by a decrease of interface state density through
out-diffusion of excess Te.
A contact process for making low-resistance contacts to polycrystalline
pCdTe has been claimed to be compatible with module fabrication needs
(McCandless et al., 1994). After CdC12 processing, the CdTe surface is coated
with a thin layer of Cu by electron beam evaporation that is then heated
and reacted, diffusing Cu into the CdTe to dope it p t y p e . The reaction re-
moves elemental Cu from the surface, that might lead t o chemically-induced
instability and produces a conductive surface that can be contacted using dif-
ferent materials. Using CdTe films from a variety of sources, qboc varied from
0.78 to 0.86 V, the fill factor from 0.71 to 0.77, and the efficiency from 11.0 to
14.1%. A related process involving the deposition of a very thin Cu,Te layer
on the CdTe surface has been described by Florez et al. (1996).
Although most polycrystalline-based devices are made with contacts that
involve Cu in some way, there are a number of alternatives. Ghosh et al. (1995)
reported making contacts with resistivities of about 0.1 ohm-cm2 by depositing
electroless Ni containing P onto a previously prepared surface.
5.3. Doping of ptype CdTe

A number of different techniques have been applied to the specific problem of
increasing and controlling the bulk p t y p e conductivity of single crystal CdTe,
which are primarily the subject of this section. We consider examples of ion
implantation doping, CVD and MOCVD doping, photon-assisted doping, dop-
ing from a CdsAs:! source, and ion-assisted doping. In polycrystalline materials
there is considerable compensation of incorporated dopants by grain boundary
states, so that the effective carrier densities can be orders of magnitude lower
then the doping density.
Ion Implantation Doping

Doping of n-type CdTe single crystals with conversion from n- to p t y p e by
standard ion-implantation of As+ and P+ has been investigated in some detail
(Chu et al., 1980). Photovoltaic CdTe homojunctions were made by implanta-
tion of As+ ions into n-type undoped Cd-annealed CdTe crystals (Chu et al.,
1978). Controlled annealing of the implanted samples with Cd overpressure
improved the doping efficiency. High values of q50c = 0.84 V were achieved, but
with low quantum efficiency resulting in a cell efficiency of only 3.0%,probably
associated with low electron diffusion lengths in the p t y p e implanted layer.
C V D and M O C V D Doping
Chu et al. (1985) reported doping of p t y p e CdTe multicrystalline films de-
posited on non-crystalline substrates from the direct combination of the ele-
ments in a CVD system using PH3 or AsH3, yielding a maximum hole density
of about 6 x 1015 cmP3. Ghandhi et al. (1987) obtained hole densities of
2 x 1017 ~ r n -in~ epitaxial films grown on single-crystal CdTe substrates at
350°C using metalorganic chemical vapor deposition (MOCVD) growth with
AsH3 as the dopant.
Photon-Assisted Doping (PAD)

Beginning in 1986, Schetzina and his co-workers pioneered a new technique
that they called Photo-Assisted Molecular Beam Epitaxy (PAMBE) in which
controlled doping of single crystal CdTe grown by MBE was obtained by illumi-
nation of the growing films (A = 0.5 p m at 100 mW/cm2) and co-evaporation
of a dopant (Bicknell et al., 1986, 1987, Hwang et al., 1988, Fahrenbruch et al.,
1992). They reported highly doped n- and p t y p e CdTe films, using In for
n-type and Sb or As for p t y p e . The highest hole density reported was for
As-doped films with p = 6.2 x 1OI8 cmP3. Films grown by this technique were
also reported to have better crystalline quality than those grown without il-
lumination. The general assumption was that illumination supplies additional
kinetic energy to the growth surface and enables enhancement of specific chem-
ical reactions and surface reactions (Benz et al., 1990). In subsequent years
the only research groups that reported successful PAD results with CdTe are
Schetzina’s group at North Carolina State University, and two groups at other
laboratories which include his former students (Myers, 1989; Harris et al.,
1990, 1991; Bicknell-Tassius et al., 1989, 1990). There appears to be agree-
ment among other workers that the use of the PAMBE technique to obtain
CdTe and HgCdTe layers yields an improvement in the structural quality of
the films with illumination during growth, but has little if any influence on
doping (Koestner et al., 1989; Arias et al., 1990; Harris et al., 1990; Tiwari
et al., 1991).
Several results indicate that Cd/Te flux ratios greater than unity during
CdTe film growth facilitate dopant incorporation and activation (Harper et al.,
1989; Bicknell-Tassius et al., 1990; Wu et al., 1991; Arias et al., 1990).
A consensus of workers in the field seems to favor the opinion that the
effect of photons is to increase the desorption rate of Te (thus creating Te
vacancies) and to enhance the surface mobility of atoms at the growing surface
(Fahrenbruch et al., 1992). Arsenic is the most widely used dopant for growth
of p C d T e by PAMBE.
Doping from a Cd3As2 Source

Co-evaporation of Cd3As2 during epitaxial film growth by vacuum evaporation
on single crystal substrates enabled incorporation of electrically active As into
CdTe films, giving hole densities up to 2 x 10l6 ~ m - whereas
~ , co-evaporation
of elemental Cd or As4 did not (Fahrenbruch et al., 1992). In general, doping
p C d T e and p Z n T e films using compound dopants sources such as Zn3Asz
and Cd3As2 has produced some interesting results. Incorporation of As into

MBE-grown ZnSe films using Zn3As2 as the As source (Shibli et al., 1990;
Turco-Sandroff et al., 1991), and deposition of a mixture of Cd3As2 As onto +
the surface of a CdTe film grown by CSVT followed by indiffusion has been
used to fabricate p n junction solar cells (Cohen-Solal, 1985).
Ion-Assisted Doping ( I A D )
In the IAD process ionized and accelerated dopant beams (usually of energy
less than 100 eV) are directed onto a film as it is being grown from the vapor.
The technique has been successfully used to control the dopant incorporation
in MBE-grown Si and GaAs (Greene et al., 1985). IAD with phosphorus
impurity to produce p t y p e epitaxial CdTe films by vacuum evaporation on
single crystal substrates has been investigated as a function of ion dose, ion
energy, growth temperature, and growth rate (Sharps et al., 1990), and an
overview given by Fahrenbruch et al. (1992). A diagram of the apparatus used
is given in Fig. 5.8. The system was designed so that the CdTe effusion cell
and the ion source were simultaneously directed onto the substrate.
I ......
,________._._...--.
,_.___.._...
i-
I
: ..
Faraday Cup and Shuner
CdTe Source
Ion S ource
Fig. 5.8. Schematic diagram of the ion-assisted doping system. (Reprinted with permission
from P. Sharps et al., J . A p p l . Phys. 68, 6406 (1990). Copyright 1990 American Institute
of Physics.)
Ion Dose ( ~ r n . ~ )
Fig. 5.9. Comparison of hole density induced in CdTe by IAD, and SIMS measurements on
incorporated phosphorus, as a function of ion dose. Squares refer to the hole density data,
and circles refer to the SIMS data. (Reprinted with permission from P. Sharps et al., J .
Appl. Phys. 68, 6406 (1990). Copyright 1990 American Institute of Physics.)
The variation of hole density and the density of incorporated P by SIMS

measurements are compared in Fig. 5.9 as a function of ion dose. The growth
temperature was 4OO0C, the ion energy was 60 eV, the growth rate was
10 pmlh, the growth time was 1 hour, and the substrates were single crystal
p t y p e CdTe. A linear dependence of hole density on ion dose is observed until
saturation occurs a t a value of p = 2 x 1017 ~ m - for
~ ;higher ion doses, the hole
density remains independent of ion dose until a dose of about 4 x lo” ~ r n - ~ ,
after which a further increase in ion dose leads to a decrease in the mea-
sured hole density. The maximum hole density corresponds well with the
maximum hole density in p t y p e CdTe single crystals observed by Selim and
Kroger (1977), for example, who found that introducing P a t levels of up
to 5 x lo1’ cmP3 into single-crystal CdTe produced a hole density of only
1 x 1017 ~ m - ~ The. parallel shift of the curves in Fig. 5.9 is probably due to
an overestimate of the electrical activity of the P in the “standard” Bridgman-
grown single-crystal sample of CdTe:P. Overall the data suggest that the elec-
trical activity of the incorporated P is approximately unity for the positively
sloped portion of the curve.
The decrease in hole density for the highest ion doses is possibly due to
more compensating damage occurring than can be annealed out at the growth
temperature. An investigation of the effects of ion bombardment of p C d T e
with Ar ions showed that the threshold for damage occurs a t a n accelerating
voltage of slightly less than 100 V, and that bombardment by Ar ions a t higher
voltages results in the formation of an n-type surface layer on the p t y p e CdTe

crystals (Chien et al., 1988).
An investigation of the effects of growth variables indicated that for the
growth conditions considered, the hole density was independent of growth tem-
perature between 350°C and 500"C, independent of the ion energy over the
range from 60-300 eV, and decreased with decreasing growth rate at a given
ion dose (Sharps et al., 1990). The films showed the same hole mobilities as for
high quality Bridgman-grown single crystals doped with P to about the same
level, and the hole lifetime for the films was about an order of magnitude larger
than that obtained for a P-doped single crystal. Unfortunately, however, the
electron minority-carrier lifetime was between three and ten times smaller than
the minority carrier lifetime in single crystals. When the ion beam current was
increased, the minority carrier lifetime decreased by another order of mag-
nitude, indicating that the IAD process itself is responsible for an increased
density of recombination centers. If these layers were to be used in a CdS/CdTe
solar cell, it would be necessary to have a two-layer structure at the CdTe sur-
face, with an IAD CdTe contact layer below an undoped light-absorbing CdTe
layer making contact with the CdS top layer. Such heterojunctions did not ex-
hibit the same decrease in J,, seen with a heterojunction prepared with doped
CdTe directly at the junction interface with CdS.
Fig. 5.10. Hole density and minority carrier diffusion length versus ion dose for IAD
pCdTe:P at 60 eV, compared to 20 eV with electron irradiation during growth. (Reprinted
with permission from D. Kim et al., J . A p p l . Phys. 7 5 , 2673 (1994). Copyright 1994
An investigation of the nature of the ion damage associated with IAD on

single crystals revealed the existence of such damage through measurements
of transmission electron microscopy, etch-pit density, and minority-carrier dif-
fusion length, and showed that the ion damage depends on both the ion dose
and the ion energy (Kim et al., 1994). Although reducing the ion energy be-
low 60 eV results by itself in lower doping densities, the use of simultaneous
electron irradiation and Cd overpressure during deposition make it possible to
achieve equivalent doping levels for 20 eV ions while reducing the ion damage.
Figure 5.10 shows the dependence of hole density and minority carrier diffusion
length on ion dose for both an ion energy of 60 eV, and for an ion energy of
20 eV with simultaneous electron irradiation and Cd overpressure. It is pro-
posed that simultaneous electron irradiation makes the surface Cd-stabilized
(Singh and Arias, 1989; Wu et al., 1991), and creates free electron-hole pairs
at the growing surface that change the Cd-Cd bond strength and enhance
Cd kinetics a t the surface (Arias et al., 1990). Figure 5.10 shows that the
minority-carrier diffusion length is three times larger when using 20 eV ions
combined with electron irradiation, compared to using 60 eV ions alone, in
achieving approximately the same hole density.
A second way to control the microstoichiometry of the CdTe surface is to
vary the Cd/Te flux ratio by applying a Cd overpressure. By using excess
Cd corresponding to Cd/Te = 1.002, together with 20 eV P ions and electron
irradiation, p C d T e : P films with p = 1 x 1017 cm-3 and L d = 0.35 pm were
obtained (Kim et al., 1994). A CdS/CdTe heterojunction with a 20 eV IAD
CdTe film showed an efficiency almost three times greater than a heterojunc-
tion made with a 60 eV IAD CdTe film.
Transport properties of IAD CdTe films deposited with either 60 eV or
20 eV were measured using the Hall effect between 8 K and 400 K , and were
compared with single crystal values (Moesslein et al., 1993). The hole mobility
in the films was essentially the same as in single crystals, and showed the same
type of temperature dependence corresponding to ionized impurity scattering
at lower temperatures and polar mode scattering at higher temperatures.
5.4. Post-Deposition Processing and Interface Properties

One of the keys to optimizing solar cells based on polycrystalline CdTe is a
postdeposition heat treatment to improve the properties of the junction inter-
face (Basol et al., 1985; Meyers, 1989; Basol, 1992; McCandless and Birkmire,
1991; Birkmire et al., 1992; Birkmire and Meyers, 1994; Ferekides et al., 1994).
Such heat treatment is usually carried out a t temperatures greater than 400°C
C a d m i u m Telluride and O t h e r II-VI Materials 155
and in a medium including CdClz and/or 0 2 . The heat treatment causes CdTe
grains to regrow and become larger, and decreases the defect density at the
junction interface. The p t y p e character of CdTe films appears to be enhanced
upon annealing in 0 2 at elevated temperatures, although the exact mechanism
is not yet understood. The importance of this processing step led to the gen-
eral recipe: “The golden rule for making CdTe devices is to deposit cadmium
and tellurium as inexpensively as possible and then t o heat-treat the devices
to activate them.” (Zweibel and Barnett, 1993). The equivalent sentiment
is pictured cartoon-style in Fig. 5.11. In some cases these treatments can be
made an integral part of the film growth process itself so that a post-deposition
step is not necessary (Mitchell et al., 1985b; Basol, 1992).
Fig. 5.11. A general recipe for the preparation of high efficiency thin film CdTe solar cells.
(Reprinted with permission from B. M. Basol, International Journal of Solar Energy, 12,
25 (1992). Copyright 1992, Harwood Academic Publisher, Langhorne, PA.)
The following design rules for preparing efficient CdS/CdTe solar cells can
be summarized (Basol, 1992). (1) The CdTe films should be deposited by
any one of several suitable procedures onto a transparent CdS/TCO/glass
substrate. Here TCO stands for transparent conducting coating, e.g. SnOz or
ITO. (2) The thickness of the CdS layer is made as thin as possible to improve
the short wavelength cell response. The thickness can easily be reduced to
below 0.2 pm using CdS deposition processes such as solution growth, elec-
troplating, and CSVT. (3) The CdTe layer is chemically treated to produce a
low-resistivity p t y p e Te-rich surface suitable for a tunneling contact with typ-
ical contact materials graphite or Ni. A p t y p e dopant such as Cu is usually
introduced at the contact/CdTe interface with an annealing step before the
contact deposition. (4) Finally a heat treatment involving 0 2 and CdC12 is an
important ingredient in the fabrication process, promoting crystal growth and
the p t y p e character of the CdTe film, as mentioned above.
The process by which an n-type, as-deposited CdTe film is converted into
p t y p e by heat treatment in air has been named the type-conversion/junction-
formation (TCJF) process. The application of the T C J F process to CdTe and
HgCdTe films produced by electrodeposition has also been described (Basol,
1984, 1988).
A two-stage deposition process has also been proposed as a possible method
for CdTe/CdS solar cell fabrication (Basol and Kapur, 1990; Bhatti et al., 1992;
Basol, 1992). This involves CdTe film growth (1) by deposition of alternating
Cd and Te layers onto a suitable substrate by such techniques as electrode-
position, vacuum evaporation, or sputtering, followed by (2) reaction of these
stacked layers to form the compound after introducing varying amounts of
CdC12 into the unreacted stacked layers to promote grain growth.
Several investigations have led to the conclusion that a CdSI-,Te, alloy is
formed at the CdTe/CdS interface due to interdiffusion that takes place during
fabrication, a process that is enhanced by the presence of 0 2 (Clemminck
et al., 1991; Birkmire et al., 1992; Mao et al., 1995; Ferekides et al., 1996).
It is believed that the formation of this interfacial layer reduces structural
defects due to lattice mismatch between the semiconductors and leads to a
lower defect density in the critical region near the interface. The extent of
interdiffusion and the value of x obtained in a particular case, depend on the
deposition temperature of CdTe and the CdC12 present during subsequent heat
treatment conditions. The tendency of 0 2 during fabrication to produce small-
grain CdS films is consistent with an enhancement of Te diffusion into CdS.
The net effect is to produce CdTe/CdS cells with higher &,c’s, fill factors, and
higher cell efficiencies.
The effect of reducing the thickness of the CdS film in polycrystalline
CdS/CdTe solar cells fabricated by vacuum evaporation, with subsequent treat-
ment with CdClz and a heat treatment in air, has been investigated (McCand-
less and Hegedus, 1991; Granata et al., 1996). Spectral response measurements
indicate that CdS and CdTe interdiffusion, corresponding to the formation of
C a d m i u m Telluride and O t h e r 11-VI Materials 157
both S-rich and Te-rich CdTel-,S, regions, increases as the CdS thickness
decreases from 1.5 to 0.12 pm. When the CdS thickness is < 0.1 pm, the
spectral response indicates the complete disappearance of a distinct CdS layer,
and the subsequent formation of a TCO/CdTel-,S, junction. In general,
the TCO/CdS,Tel-, junction is inferior to that involving CdS, so shunt cur-
rents are increased as CdS thickness is decreased. There are some exceptions
(Mitchell et al., 1985b; Nakazawa e t al., 1987), suggesting that with proper
treatment of the TCO (e.g. formation of a n insulating layer of TCO a t the
interface) & can be maintained for very thin or non-existent CdS. A related
investigation of the effect of CdS thickness on CdS/CdTe quantum efficiency
suggests that the difference between thick and thin CdS might well be as much
as 12% versus 15% in device efficiency (Granata et al., 1996).
0.1 0.2 0.3 0.4 0.5

ATOMIC COMPOSITION X
Fig. 5.12. Measured band gaps of as-deposited CdTel-,S, thin films as a function of x, as
reported in this work (X), Bonnet 1970 (triangles), Hill and Richardson 1973 (diamonds),
Ohata et al., 1973 (circles), and Al-Ani et al., 1993 (squares). (Reprinted with permission
from D. G . Jensen et al., in T h i n Films f o r Photovoltaic and Related Device Applications,
eds. D. Ginley, A. Catalano, H. W. Schock, C. Eberspacher, T. M. Peterson and T. Wada,
Materials Research Society Proc. 426, Pittsburgh, PA (1996a), p. 327.)
Predominantly single-phase CdTel-,S, films with 0 5 2 5 0.45 were grown

by vacuum co-evaporation of CdS and CdTe, with the dependence of band
gap on z shown in Fig. 5.12 (Jensen et al., 1996a,b). Phase segregation was
promoted by heat treatment of the films at 415°C in the presence of CdClz, and
the solubility limit of S in CdTe was determined t o be 5.8%. CdTel-,S,/CdS
solar cells made with compositionally uniform CdTel-,S, layers with 2 near
the solubility limit, gave an efficiency of 10.8% and showed cell characteristics
very much like those of a conventional CdTe/CdS cell where the alloy is formed
by cell processing.
Transmission electron microscopy (TEM) was used to investigate the mi-
crostructures and interfaces of thin film CdTe/CdS/ITO/glass photovoltaic de-
vices, particularly as a result of annealing in air after prior exposure to CdCl2
(Loginov et al., 1996). The cells used were prepared by vacuum evaporation of
CdS onto an ITO/glass substrate, followed by CSVT deposition of CdTe. It
is concluded that a CdC12 treatment reduces the influence of interfacial states
on the current transport mechanism (changing from tunneling to thermally
activated), causes grain growth in the CdS and CdTe, and decreases the den-
sity of stacking faults and dislocations in the CdTe. It also introduces C1-rich
precipitates into the lattice, but these have not been observed in the region
near the interface, and their effect on device performance remains unknown.
TEM indicates that the CdTe grains grow epitaxially on the CdS grains
during deposition and that heat treatment causes substantial grain growth in
the CdTe, such that the epitaxial relationship is lost and one CdTe grain may
bridge several differently oriented CdS grains (Al-Jassim et al., 1993).
An investigation of the micro through nanostructure properties of polycrys-
talline CdTe using atomic force microscopy (AFM) has shown correlations with
processing and electronic structures for several standard deposition techniques
such as vacuum evaporation, CSVT, and sputtering (Levi et al., 1994). Corre-
lations between nanostructure and optical properties indicate that CdC12 heat
treatment passivates defects. Except for CSVT-deposited films, the CdCl2
treatment also enhances grain size. Diffusion of sulfur across the CdTe/CdS
interface during heat treatment has been verified.
The CdClz anneal of CdTe/CdS solar cells usually consists of coating the
CdTe surface with a saturated solution of CdC12 in methanol and heat treating
the film in air at 400°C to 450°C for 10 to 30 minutes. An alternate approach
using a CdClz vapor treatment has been developed that results in uniform
large grain films, preferred (111) crystallographic texture, less chloride surface
residue, less S diffusion into the CdTe, and more reproducible current-voltage
performance than is obtained with other CdC12 treatments (Zhou et al., 1994;
Birkmire et al., 1995; McCandless et al., 1996). In the vapor treatment, sam-
ples were annealed at 425°C for 20 minutes in air with a partial pressure of
CdC12 of 0.04 Torr. Vapor treated films do not require a rinse step prior to
device completion, unlike samples that are CdCl2:methanol treated. Solar cells
prepared with the CdClz vapor treatment were comparable to the best CdTe
cells: & = 0.83 V, J,, = 19.6 mA/cm2, and f f = 0.65. Similar microstruc-
tural changes were observed for HC1 vapor treatment of films (Qu et al., 1996).
Interdiffusion between CdS and CdTe during cell preparation has been
deliberately limited by a process in which the CdS film on a glass substrate
is treated with ZnC12 and CdClz to reduce the reactivity of the CdS when
CdTe is subsequently deposited on top of the CdS by close-spaced sublimation
(Romeo et al., 1997). Resulting cells showed &, = 0.845 V, J,, = 23 mA/cm2,
f f = 0.71, and efficiency of 13.8%.
The need to evaluate the uniformity of the microstructure of CdS/CdTe
large-area solar cells has led to application of the non-destructive testing
method of time-resolved photoluminescence to map recombination lifetimes
in such cells (Ahrenkiel, 1992; Ahrenkiel et al., 1994). Typical lifetime profiles
indicated spatial variation by factors of two to three across 1 cm dimensions,
and that the open-circuit voltage of the cells was controlled by the area with
the minimum lifetime.
5.5. SIS Junctions
One possible solution to the problems posed by difficulties with doping and
contacts on p C d T e has been proposed by Meyers (1989). The solar cell consists
of a p i - n heterojunction made up of n-CdSli-CdTelpZnTelNi, as shown
in Fig. 5.13. The n-CdS layer is deposited on SnOz-coated glass, the CdTe
r
V
-SnO, - 0.4 pm
-CdS - 0.15 prn
-CdTe - 2 0 pm
t -2nTe-0.1
- - prn
Ni 0.05 prn
Fig. 5.13. Solar cell structure for an 11%CdTe n - i p solar cell. At 1 sun,
# = 0.68 V,
J ~ ~
Jsc = 20.5 mA/cmZ, fill factor = 0.625. (Reprinted with permission from P. V. Meyers,
Photovoltaics Advanced Research and Development (1989), 9th Annual Review Meeting,
SERI/CP-213-3495, p. 19. Copyright 1989, SERI, Golden, CO.)
layer is deposited by electrodeposition on the CdS, and the final ZnTe layer is
deposited on the CdTe. Work on this kind of cell has been extended by Nouhi
et al. (1989) with the use of CdTe films deposited by MOCVD to achieve
small-area cells with an efficiency over 9%.
SIS-type cells have also been prepared with polycrystalline ZnCdTe or
CdMnTe (Rohatgi et al., 1988, 1989) as the i-region material; these devices
have a lower 4octhan similar devices using CdTe alone.
5.6. Grain Boundary Effects

The effect of grain boundaries on the electrical transport properties of poly-
crystalline n-type CdTe films doped by coevaporation of In was examined
by comparing the properties of polycrystalline films evaporated by HWVE on
glass, with those of epitaxial films evaporated by HWVE on BaFz single-crystal
o ON GLASS
\
8\, LIGHT ?
0
10' - \
L I I I I
370 470 5 70
670
INDIUM SOURCE TEMPERATURE ("C)
Fig. 5.14. Dark and light resistivity of CdTe:In films grown on glass and on single crystal
BaFz by HWVE, as a function of the indium source temperature. Films on glass in the
dark ( 0 ) and in the light (0);films on BaF2 grown with Ts,,b = 480OC in the dark (A) and
in the light (A); films on kaFz grown with T S U b = 450OC in the dark (D) and in the light
(0). (Reprinted with permission from W. Huber et al., J. A p p l . Phys. 54, 4038 (1983).
Copyright 1983 American Institute of Physics.)
ON GLASS
-104
-
0
-lo3 5
.
n
-=L
E
0
-lo2 >
c2
-
m
0
-10' =
RESISTIVITY p ( R cm)
Fig. 5.15. Variation of the electron density and mobility under optical excitation as a function
of the resistivity in the light for CdTe films deposited by HWVE (a) on glass substrates, and
(b) on a BaFz substrate. (Reprinted with permission from W . Huber et al., J . Appl. Phys.
54, 4038 (1983). Copyright 1983 American Institute of Physics.)
substrates (Huber e t al., 1983). Resistivity and Hall effect measurements could
be successfully interpreted in terms of the grain boundary model first proposed
by Set0 (1975), which is a one-dimensional model including the contribution of
the bulk resistivity of the undepleted portion of the grain, and carrier transport
across the barrier described by thermionic-diffusion theory (Sze, 1969).
The dependence of the dark and light resistivity of the two types of films
on the temperature of a n indium source used for doping is shown in Fig. 5.14,
and the variation of the electron density and mobility under photoexcitation,
measured by photo-Hall effect, with the light resistivity for the two types of
films is shown in Fig. 5.15. The dark resistivity of CdTe films deposited on
glass is uniformly high. Photoexcitation causes the resistivity to decrease by

orders of magnitude by a process in which the electron density is increased
but the mobility is unchanged. These effects are consistent with the existence
of fully depleted grains in these films (grain size about 1 pm) in the dark, as
described by the models of Card and Yang (1977) and Seager (1981).
The dark resistivity of CdTe films deposited on BaFz single crystal sub-
strates under the same HWVE deposition conditions is orders of magnitude
smaller than that for films deposited on glass. Photoexcitation produces a
change in electron mobility but not in electron density. These effects are con-
sistent with the existence of partially depleted grains in these much larger-grain
films.
The optical and electrical properties of grain boundaries in n- and p t y p e
CdTe have been investigated by analysis of single boundaries within bicrystals
and of polycrystalline thin films (Thorpe et al., 1986). Figure 5.16 shows the
temperature dependence for conductivity in dark and light of a single grain
boundary in a p t y p e CdTe bicrystal. Grain boundaries control the magnitude
Fig. 5.16. Grain-boundary conductivity as a function of temperature in the dark and for
several different illumination intensities (10 = 60 mW/cm2 white light) for the grain bound-
ary in a p t y p e CdTe bicrystal. The inset shows the variation of the activation energy with
light intensity at low temperatures. (Reprinted with permission from T. P. Thorpe et al., J .
A p p l . Phys. 60, 3622 (1986). Copyright 1986 American Institute of Physics.)
of the mobility of majority carries in polycrystalline CdTe, with resistance val-

ues associated with grain boundaries being 3 to 5 orders of magnitude larger
than expected for bulk material. At higher temperatures the grain bound-
ary conductivity is not affected by illumination, but at Iower temperatures
the grain boundary conductivity is thermally activated with an activation en-
ergy that decreases with illumination. The results appear to be consistent
with an interpretation that proposes thermally-assisted tunneling in the low-
temperature range and thermal excitation over the boundary barrier at higher
temperatures, as earlier proposed for the temperature dependence of the mo-
bility in PbS (Espevik et al., 1971) and CdS (Wu and Bube, 1974) due to grain
boundary effects.
The energy dependence of the grain-boundary state densities was deter-
mined for CdTe bicrystals by boundary J-4 dependence following the method
of Pike and Seager (1979) for states above the valence band, and by spectral
response measurement of boundary photocapacitance and/or photoconductiv-
ity using the method developed by Werner et al. (1982) for states below the
wz --After H2 Diffusion
10’30 0.2 0.4 0.6 0.8 1.0 1.2 4

(E-E,). ev
Fig. 5.17. Density of grain-boundary interface states as a function of energy in the forbidden
gap of CdTe, for a particular p t y p e CdTe bicrystal, before any passivation, after passivation
by Li diffusion and after passivation by hydrogen heat treatment. (Reprinted with permission
from T. P. Thorpe et al., J . Appl. Phys. 60,3622 (1986). Copyright 1986 American Institute
of Physics.)
conduction band (Thorpe et al. 1986). Figure 5.17 shows a typical variation
of grain boundary state density without any passivation, and the effects of
Li diffusion and H2 heat-treatment passivation. The passivation effects are
striking, but unfortunately are not stable for more than a few weeks. Similar
experiments with grain boundaries in n-type CdTe showed that in this case
passivation could be temporarily achieved by heating in air, not in H2.
5.7. Film Deposition by Vacuum Evaporation

An n-CdSlpCdTe solar cell with an efficiency of 7.9% (+,= = 0.63 V, J,, =
16.1 mA/cm2, ff = 0.66, J , = 1.7 x A/cm2) was prepared by vacuum
evaporation (VE) of an n-CdS film on prepared p C d T e single-crystal sub-
strates (Mitchell et al., 1977b). Optical absorption coefficients of CdTe greater
than l o 4 cm-I were calculated from the photovoltaic spectral-response curve
10:
CdS- -CdTe
10'
I
(A)
16'
lGf
Id' I I I 1 I I
1 2.0 1.00 1.0 2.0 3.0

DISTANCE FROM JUNCTION ( p m )
Fig. 5.18. Electron-beam-induced current a s a function of beam position for the 7.9% n-
CdSlpCdTe cell. The calculated values of the minority carrier diffusion lengths are 0.40 pm
in pCdTe, and 0.43 p m for n-CdS. (Reprinted with permission from K. W. Mitchell et al.,
J . A p p l . Phys. 48, 4365 (1977). Copyright 1977 American Institute of Physics.)
(Mitchell et al., 1977c), and an analysis of the fill-factor in such cells was car-
ried out (Mitchell et d., 1977a). Sputtered indium-tin-oxide (ITO) was used as
a transparent electrode to the CdS, and glycerol was used as a n anti-reflection
coating. Two CdTe surface treatments were compared (mechanical polish-
ing, and mechanical polishing followed by a bromine-in-methanol (MB) etch),
and the effects of different CdTe and CdS resistivity were investigated. The
MB-etched cells were significantly better than the mechanically polished cells,
giving a saturation current J , some one to two orders of magnitude smaller,
and a quantum efficiency significantly larger. A typical spectral response of
the cells is shown in Fig. 1.13in Chapter 1 of this book, and a plot of electron-
beam-induced current (EBIC) for the 7.9% cell is given in Fig. 5.18.
A variation of vacuum evaporation called hot-wall vacuum evaporation
(HWVE) is illustrated in Fig. 5.19, similar to that used by Lopez-Otero (1978)
and Lopez-Otero and Huber (1979). The apparatus fits inside a standard
vacuum system, and consists of a heated quartz liner with three independent
furnaces that allow an independent control of the CdTe, dopant, and Cd or
Te source materials. The substrate is placed in a fourth furnace on top of
the quartz liner. The use of a heated wall confining the region of evaporation
almost eliminates waste of material and provides an environment in which the
deposited films are closer to equilibrium conditions. Many of the phenomena
encountered in depositing CdTe films are similar using CSVT or HWVE. In-
vestigation of grain boundary effects using CdTe films deposited by HWVE is
described above (Huber et al., 1983).
Polycrystalline CdTe films were deposited by HWVE on graphite sub-
strates, and single-crystal CdTe films were deposited by HWVE on single-
crystal pCdTe:P substrates (Fortmann et d., 1987). CdS/CdTe heterojunc-
tions were formed by the vacuum evaporation of CdS. It was observed that the
q50c was a maximum at about 0.80 V for both types of cells when the carrier
densities in the n-CdS and p C d T e were approximately equal. The effects were
successfully modeled in terms of an unidentified level lying 0.45 eV below the
bottom of the conduction band in CdTe.
Difficulties in doping CdTe films using a doped source, such as are described
below for CSVT film deposition (Anthony et al., 1985), were also encountered
with attempts to dope CdTe using HWVE (Huber et al., 1983; Anthony et al.,
1984; Bube et al., 1984). Attempts were made to dope CdTe films by co-
evaporation of such dopants as As, Sb, Na, and Ag, but all attempts to dope
p t y p e CdTe films during HWVE deposition were unsuccessful. Likely causes
include: (1) small sticking coefficients for the dopants on the growing surface
Thermocouple Hook (Up and down

Position and/or side-to-side
8
strale Carrier
F n 1 Zone
(Substrate) Shutter Guide
huller (Ouarlz)
Source Bottle IOuartz)
Secondzone
(Source) CdTe Source Material
Third Zone
1 Second Source (Dopant)
I
Radlalton Shields
Heater Wound on
tainless Steel Core
Fourth Zone Third Source (Cd or Tel
Threaded Rod Supports
Thermal Links lo H 0
Cooled Baseplate
Fig. 5.19. Schematic diagram of the hot-wall vacuum evaporation (HWVE) apparatus used
to grow CdTe thin films. The chamber pictured is enclosed in a vacuum system. (Reprinted
with permission from R. H. Bube et al., I E E E Transactions on Electron Devices ED-31,
528 (1984). Copyright 1984, IEEE, NY.)
of CdTe a t elevated temperatures, ( 2 ) evaporation of many of these dopants as

molecular species such as As4 or Sb2 with high dissociation energies, (3) self-
compensation in CdTe, and (4) impurities being incorporated on more than
one site, giving rise to amphoteric behavior.
As mentioned in Table 5.2, an ITO/CdTe heterojunction fabricated by e-
beam evaporation of IT0 on single-crystal p C d T e gave q50c = 0.81 V, J,, =
20 mA/cm2, and an efficiency of 10.5% (Werthen et al., 1983b). Nakazawa
et al., (1987) fabricated InzO3/CdTe cells on single-crystal CdTe with &c =

0.89 V, J,, = 20.1 mA/cm2 and efficiency of 14.4%. The I n 2 0 3 layer was vac-
uum deposited directly on the CdTe single crystal by reactive vacuum evapo-
ration of In in 0 2 and ultrasonic cleaning was required during etching for the
highest 4ocvalues (to 0.91 V). These are the highest 4ocvalues observed to
date for CdTe-based cells.
5.8. F i l m D e p o s i t i o n by Close-Spaced Vapor Transport ( C S V T )

[or Close-Spaced S u b l i m a t i o n (CSS)]
In the CSVT method, sometimes called close-spaced sublimation (CSS), ma-
terial is transported from a source wafer to a substrate through a gas at atmo-
spheric pressure. The source and substrate are in contact with carbon blocks
that are heated by infrared lamps. The source and substrate are generally held
about 1.5 mm apart by quartz spacers.
CSVT was first used by NicoIl(l963) for the heteroepitaxial growth of GaAs
on Ge. Since then it has been used to grow a wide variety of semiconductors,
as summarized by Anthony et al. (1984) in their investigation of the growth
process itself.
Early investigations of p C d T e films deposited on single crystal n-CdS by
the technique of close-spaced vapor transport are described by Saraie et al.
(1972), Fahrenbruch et al. (1974), and Buch et al. (1977). One of the striking
lo-" 16. lo* to-.

REVERSE SATURATION CURRENT, Alcm'
Fig. 5.20. Equiefficiency curves for the pCdTe/n-CdS heterojunction system as a func-
tion of quantum efficiency and reverse saturation current density. Calculated for negligible
reflection, series resistance and area utilization losses. (Reprinted with permission from
A. L. Fahrenbruch et a!., Appl. Phys. Lett. 25, 605 (1974). Copyright 1974 American
Institute of Physics.)
QUARTZ-HALOGEN
Fig. 5.21. Basic features of the close-spaced vapor transport (CSVT) system used t o grow
CdTe thin films. (Reprinted with permission from T. C. Anthony et al., J . Vac. Sci.
Technology, A2, 1296 (1984). Copyright 1984, American Institute of Physics.)
consequences of this early research was the realization that the reverse satu-
ration current density J , was about lo3 times larger than the lowest values
observed for junctions prepared by other means, resulting in values of open-
circuit voltage between only 0.5 and 0.6 V instead of the highest observed value
of about 0.9 V. Figure 5.20 shows the dependence of cell efficiency on quan-
tum efficiency and J , for pCdTe/n-CdS heterojunctions; for these early cells
prepared by CSVT, the quantum efficiency was about 0.85 and J , was about
3x A/cm2. Use of CSVT for the growth of CdTe films has also been
reported by Mimila-Arroyo et al. (1977, 1979) and Tyan and Perez-Albuerne
(1982).
A diagram of the CSVT apparatus used by Anthony et al. (1984) is given
in Fig. 5.21. The source and substrate susceptors, as well as the mask, are ma-
chined from purified, high-density graphite. Ceramic-sheathed chromel-alumel
thermocouples monitor the temperatures of the graphite blocks that are heated
independently by two 650 W quartz-halogen lamps. A stainless-steel cooling
tube positioned within the substrate block enables lower substrate tempera-
tures to be achieved and permits rapid cooling of the substrate. In addition,
C a d m i u m Telluride and Other IZ-VI Materials 169
the spring action of the cooling tube ensures good thermal contact between
the substrate and the substrate block. A perforated] cylindrical quartz spacer
maintains a separation of about 1 mm between the source and substrate. The
graphite source block is supported by a quartz plate and the entire chamber
is enclosed within a quartz tube. It was concluded that the growth of CdTe
films by CSVT in inert ambients at atmospheric pressure is diffusion limited.
Important parameters in the diffusion theory are the spacing, ambient gas,
ambient gas pressure, and source temperature, each offering independent con-
trol over the growth rate. Approximately equal growth rates in He and in H2
indicated the relative ineffectiveness of Hz as a transport agent for CdTe.
In a subsequent investigation of the electrical properties of CdTe films and
junctions] polycrystalline films of p C d T e were deposited by CSVT on graphite
1.10 1.18 1.26 1.34

i /x103
~(OK) ~ ~ ~
Fig. 5.22. Uncompensated ionized acceptor density in CdTe films deposited by CSVT as
a function of the graphite substrate temperature, using a source temperature of 653OC
in hydrogen at 1 atm, for several different sources doped as indicated. (Reprinted with
permission from T. C. Anthony et al., J . Appl. Phys. 57, 400 (1985). Copyright 1985
substrates, and homoepitaxial films on single-crystal CdTe:P substrates, with

hole densities as high as 1.5x 10l6 cm-3 without intentional doping of the films
(Anthony et al., 1985). Investigation showed that this doping in the films was
controlled neither by dopant transport from the source nor by impurities in
the CSVT system. The first of these conclusions is dramatically illustrated
in Fig. 5.22 showing the uncompensated acceptor density as a function of
substrate temperature for a variety of sources containing Cs, Au:P, P, As or
no dopant. The acceptor density increases with substrate temperature, but is
independent of the doping of the source or the growth rate. The results can be
consistently interpreted in terms of the creation of intrinsic acceptor defects
significantly affected by self-compensation by other intrinsic defects (with no
incorporation of the dopant species).
CdS/CdTe/graphite solar cells were prepared using these CdTe films, with
the most efficient having &, = 0.52 V, J,, = 17.4 mA/cm2, fill factor = 0.64,
and solar efficiency = 6.4%. The effects of the three problems with CdTe
cells enumerated at the beginning of Sec. 5.2 are all clearly illustrated by the
properties of these particular cells. The fill factor decreases as the hole density
in the CdTe decreases, because of the effects of series resistance associated both
with the grain-boundary resistance of the CdTe film and the back contact
CdTe/graphite resistance. Analysis of current-voltage dependence indicates
that the transport process is controlled by recombination at interface states
above room temperature, and by tunneling below room temperature.
As early as 1982 Tyan and Perez-Albuerne (1982) showed that the CSVT
technique could be used to produce efficient CdTe solar cells. Both CdS and
CdTe layers were deposited by CSVT to form a glass/In203/CdS/CdTe/Au
cell with & = 0.75 V, J,, = 17 mA/cm2, and an efficiency of 10.5%. In
one of the first mentions of the apparent importance of oxygen in CdS/CdTe
solar cell preparation, it was reported that a small concentration of oxygen
introduced during the deposition enhanced the p t y p e character of the CdTe
film and ensured a shallow junction between the CdS and the CdTe.
Chu et al. (1987) used the CSVT technique to produce higher efficiency
CdS/CdTe heterojunction cells with the structure glass/SnO2/CdS/CdTe/
graphite:Cu with the parameters given in Table 5.2. An important step used
by Chu et al. in their preparation technique was to include an in situ cleaning
step for the CdS/SnOa/glass structure in the CSVT apparatus by heating in a
hydrogen atmosphere before depositing the CdTe; a t room temperature, values
of Jo were two orders of magnitude smaller for cells with in situ cleaning than
for cells without such a cleaning step. In both the work of Tyan and Albuerne
(1982), and of Chu et al. (1987), it appears that the inverted configuration
(CdTe on CdS, rather than CdS on CdTe) allows fine tuning of the junction
parameters to achieve higher cell performance.
Although almost all workers have found the CdS layer to be necessary
for high &, it is possible to make cells without it. Mitchell et al. (1985b)
deposited polycrystalline CdTe directly on tin-oxide coated glass by CSVT.
These 4 cm2 cells produced doc= 0.66 V, J,, = 28.1 mA/cm2, and an efficiency
of 10.5%.
The effect of various deposition parameters on CdS films deposited by
CSVT on Corning 7059 glass, and the subsequently formed CdTe/CdS junc-
tion, finally resulting in an efficiency of 15.8%, has been investigated in some
detail using measurements of SEM, photoluminescence, current versus voltage
versus temperature, spectral response, and capacitance versus voltage mea-
surements (Ferekides et d., 1993, 1996). It was found that the presence of 0 2
during deposition of CdS produced smaller and denser grains in the CSVT-
deposited CdS films, resulted in a considerable decrease in the deposition rate
that could be compensated for by raising the source temperature, and resulted
in improved solar cell performance. Measurements indicate that this is the
result of the addition of 0 2 forming pinhole free, thin (70-80 nm) CdS films,
eliminating the possibility of the subsequently deposited CdTe coming into
direct contact with the SnO2/glass substrate. The inclusion of 0 2 in the de-
position also appears to enhance the formation of a CdSI-,T, region due to
Te diffusion into the CdS films, which shifts the electrical junction away from
the metallurgical interface, as discussed above in Sec. 5.2.
There still appears to be incomplete agreement on the necessity for 0 2 ,
however. CdS/CdTe solar cells have been prepared by CSVT with an effi-
ciency of 13% without the inclusion of any oxygen in a He-only ambient by
using thicker CdTe films to minimize pinholes, and a stronger CdClz anneal
to increase interdiffusion a t the CdS/CdTe interface. (Rose et al., 1996a,b).
By modifying the source and substrate temperature profiles used during
CSVT deposition, it has been shown that it is possible to grow large-grain
material, fill pinholes, improve device &,-, and achieve a n efficiency of 12% (Li
et al., 1996).
5.9. Film Deposition by Spray Pyrolysis (SP)

The technique of spray pyrolysis (Chamberlin and Skarman, 1966) was used
to prepare n-CdSlpCdTe heterojunction solar cells by SP deposition of CdS
films on single-crystal CdTe to yield solar efficiencies greater than 6% without
HEATER s
Fig. 5.23. Schematic diagram of a spray-pyrolysis (SP) apparatus (Reprinted with permission
from Y . Ma, Ph.D. Dissertation, Stanford University (1977).)
optimization (Ma et al., 1977a). A schematic diagram of the apparatus is

given in Fig. 5.23. The reacting species are carried to the substrate in droplets
of liquid sprayed on a hot substrate. The liquid is often an organic complex
containing the material to be deposited, diluted in water and/or alcohol; in the
case of CdS for example, the organic used to supply the sulfur is thiourea, and
CdClz is used to supply the cadmium. The major advantage of spray pyrolysis
is its ability to produce thin films with good uniformity and adherence over
large areas economically.
A detailed investigation of the properties of CdS films deposited by SP was
carried out by showing that the optical and electrical properties of these films
are strongly influenced by substrate temperature, cooling rate, spraying rate,
and post-deposition heat-treatments (Ma and Bube, 1977b). It was possible
to prepare a wide variety of films with room temperature conductivity be-
tween lop4 and 10' (ohm-cm)-' , corresponding to effective electron mobilities
between and 10' cm2/V-sec.
C a d m i u m Tellurzde a n d O t h e r 11-VI M a t e r i a l s 173
Fig. 5.24. Spectral response of quantum efficiency for three cells of n-CdSlpCdTe prepared
by SP deposition of CdS onto single-crystal pCdTe. Sample M-2 used one CdTe boule,
samples M-8 and M-14 used a second boule. CdTe substrate temperature was 45OOC for
M-2 and 400OC for M-8 and M-14. HZ heat treatment was for 5 min at 400OC for M-2 and
M-8, and for 5 min at 42OOC for M-14. Solar efficiency of M-2 was 6.5% (uncorrected for
reflection losses). (Reprinted with permission from Y . Y . Ma et al., A p p l . P h y s . Lett. 30,
422 (1977). Copyright 1977 American Institute of Physics.)
Significant variables in the deposition are the temperature of the substrate

and the effects of a subsequent heat treatment in H2, which reduces the CdS
resistivity and improves the solar efficiency. Typical variations in spectral
response for three cells are shown in Fig. 5.24. All show response typical of
a buried homojunction with very long diffusion length (sharp high shoulder
on the long wavelength side). They show progressively more loss due to front
surface recombination.
One of the advantages of the SP method is the relative ease with which
solid-solution films can be prepared by a simple mixture of the components in
the appropriate ratios. A complete range oi solid-solution films was prepared
by SP for CdS,Sel-, and Zn,Cdl-,S (Feigelson et al., 1977). In both the
CdSSe and ZnCdS systems, complete solid solut!ons are formed over the entire
composition range and the lattice parameters follow Vegard’s law. In the
CdS,Sel-, system, the film resistivity is controlled by chlorine donors and
does not vary appreciably with x; in the Zn,Cdl-,S system, however, the
resistivity increases almost exponentially from about 10 ohm-cm for 5 = 0 to
10" ohm-cm for x = 1.0, due both to a n increase in the ionization energy
of chlorine donors and to compensation of these donors with increase in x
(Chynoweth and Bube, 1980).
A series of photovoltaic heterojunctions of the type n-Zno.lCdo.gS/pCdTe
have been prepared by SP of ZnCdS films on single-crystal CdTe with variation
of the CdTe substrate temperature and of the postdeposition heat-treatment
temperature in hydrogen (S.-Y. Yin et al., 1978). Results indicated that the
heterojunction system itself could provide &c = 0.8 V with an efficiency of 8%
without an antireflection coating if the technological problems associated with
the contacts to the ZnCdS film could be resolved.
A detailed investigation was made of the electrical and photovoltaic pro-
perties of heterojunctions prepared by SP deposition of thin ZnO films on
single-crystal p t y p e CdTe:P (Aranovich et al., 1979, 1980), using the sub-
strate temperature and the postdeposition temperature for annealing in H2 as
the principal experimental variables. In spite of a large 28% lattice mismatch
between ZnO and CdTe, high quantum efficiencies were achieved with values
greater than 90% if a reverse bias was applied, the spectral response is that ex-
pected for a heterojunction, and cells with efficiency up to 8.8% were obtained
referred to the active area of the cell. A thermally-assisted tunneling model
(Padovani and Stratton, 1966) in which bulk and interface deep traps control
the forward characteristics provides a good correlation with experimental data.
Spray pyrolysis has been used for the production of relatively large area
SnO,/CdS/CdTe/Ni/Sn solar cells, with small area samples showing efficien-
cies greater than 12% (Albright et al., 1988, 1989; Jordan et al., 1988).
It has been shown that CdTe films and a CdS/CdTe heterojunction can
be deposited on stainless-steel substrates using spray pyrolysis, although con-
siderable refinements would be required for a viable solar cell (Berry et al.,
1990).
It has been proposed that high-quality CdTe films can be produced by
SP using nanoparticle precursors making possible materials with improved
smoothness, density, and a lower processing temperature (Schulz et al., 1996).
CdI2 was reacted with NazTe in a methanol solvent, resulting in the formation
of soluble NaI and insoluble CdTe nanoparticles. CdTe thin films were pro-
duced by spray depositing the nanoparticle colloids (2.5-7.5 nm diameter) onto
substrates at 280-440°C with no further thermal treatment. A layer-by-layer
film growth mechanism was proposed for such a one-step spray deposition of
nanoparticle precursors.
Cadmium Telluride and Other It-VI Materials 175
5.10. Other Film Deposition Methods

Chemical Vapor Deposition (CVD)
The first CdS/CdTe heterojunction solar cell with an efficiency of 5-6% was
made by Bonnet and Rabinhorst (1972) by CVD techniques.
The possibility of fabricating n-ZnOlpCdTe solar cells by the deposition
of n-ZnO single crystal films on p C d T e single crystal substrates by chemical
vapor deposition (CVD) has been investigated by Kimata et al. (1984). The
(111) Cd surface was used as the growth surface to avoid growing ZnTe at the
interface. The efficiency was limited to 2.2% because of the effect of interface
states and the high electrode resistance to the pCdTe.
Nishimura and Bube (1985) showed that CVD deposition of CdS on single-
crystal CdTe in hydrogen, under conditions in which there is out-diffusion of
acceptors and large decrease in hole density near the surface for the uncovered
CdTe surface, reduced the loss of acceptors by serving as a diffusion barrier.
CdS/CdTe and CdS:In/CdS/CdTe heterojunctions formed in this way showed
solar efficiencies between 8 and 10%. In both n-and p t y p e CdTe, heat treat-
ment results in a reduction of carrier density near the surface. In n-type CdTe
this effect is attributed to the creation and inward diffusion of Cd vacancies,
but in p t y p e CdTe, Kim et al. (1988) have shown that the effect in P-doped
p t y p e CdTe is associated with the formation of compensating P C d anti-site
donor defects.
Screen Printing (ScP)

Reasonably efficient solar cells have been prepared from CdS and CdTe by
simple screen printing techniques (Nakayama et al., 1976, 1980; Uda et al.,
1982). A 20 pm layer of 0.2 ohm-cm CdS was screen printed onto an Inz03-
coated glass substrate, using a CdS paste obtained by mixing CdS powder with
9% by weight CdClz powder to serve as flux and propylene glycol to serve as
binder. This was followed by the screen printing of a 10 pm layer of 0.1-1 ohm-
cm, n-type CdTe, using a paste of (Cd + Te) prepared by mixing the powdered
elements and adding 0.5% by weight of CdClz powder and propylene glycol.
The layers were sintered in close-fitting (but not leak-tight) boxes in air. A
layer of Cu,Te was formed on the n-CdTe by the dipping process and Ag-paint
electrodes were applied to the Cu,Te. An efficiency of 8.1% was reported for
a cell for which an EBIC scan indicated that the electrical junction did not
coincide with the CdS/CdTe interface. The observation that the efficiency is
sharply peaked for a sintering temperature of 620°C suggests that the need
to optimize the thickness of a CdS,Tel-, layer a t the interface may be a n

important factor. Small screen-printed cells of this type have been extensively
used in calculators, and are the only CdTe cells that are sold commercially at
this writing. Developments in this area have been described by Ikegami (1988)
and Kim et al. (1994). Screen printing techniques have also been used t o
investigate the properties of CdS,Tel-, solid solutions (de Melo et al., 1994).
Electrodeposition (ED)
It was discovered early that reasonably efficient CdTe solar cells could be fabri-
cated using the relatively simple techniques of electrodeposition (Basol, 1988;
Meyers, 1988). Panicker et al. (1978) laid the foundation for this by showing
the feasibility of electroplating CdTe thin films. Fulop et al. (1982) produced
an MIS cell involving an n-CdTe film deposited by cathodic electrodeposi-
tion from an acidic aqueous solution of Cd- and Te-containing ions, and a n
insulating oxide layer obtained by annealing in air after deposition. The elec-
trodeposition technique has been developed by Basol et al. (1985), Meyers
(1989), Das and Morris (1992), Woodcock et al. (1993, 1994), and Paulson
et al. (1994). Lincot et al. (1995) have investigated the epitaxial electrode-
position of CdTe films on InP; the presence of a thin layer of CdS, formed by
chemical bath deposition on the InP markedly improved the epitaxial growth
of the CdTe.
An investigation of the formation of CdS/CdTe solar cells using the tech-
niques of electrodeposition resulted in a cell with an efficiency of 11.0% (Kim
et al., 1994a). CdS layers were deposited by chemical bath deposition on
Sn02-coated glass substrates, using cadmium acetate, ammonium acetate and
ammonium hydroxide as described by Chu et al. (1992). A CdCl2 coating
was applied to the surface of the CdS, the sample was annealed at 450°C for
50 min in N2, and then was rinsed in hot DI water and dried in Nz. The CdTe
deposition was done in an electroplating system with Cd and Te anodes, a
Ag/AgCl reference electrode, and the sample substrate as the cathode; after
deposition the CdTe samples were rinsed in hot DI water and dried in NZ. A
CdC12 coating was applied to the CdTe surfaces, samples were annealed at
410°C for 45 min in air, cooled, rinsed and dried. Contacts to the CdTe were
made by evaporating Au through masks to form dot cells (0.033 cm2) after
etching with Br-MeOH. Contacts to the CdS were made by indium solder and
silver paint. EBIC measurements indicated a maximum inside the CdTe layer,
suggesting a buried homojunction.
C a d m i u m Telluride and Other IZ-VI Materials 177
Kim et al. (1994b) also investigated the effect of annealing on the mi-
crostructure and stress state of electrodeposited CdTe, involving recrystalliza-
tion and grain growth. Additional discussion of stress testing of cells has been
given by Meyers and Phillips (1996).
Using a similar approach, Kampmann et al. (1995) carried out a detailed
investigation of the influence of the electrodeposition potential on the optical,
photoelectrochemical, and structural properties of CdTe. An efficiency of over
12% has been reported for thin film cells fabricated using electrodeposition
(Song et al., 1996).
CdS films of device quality were deposited by electrodeposition by electrore-
duction of Cd and S at the substrate in a bath of CdClz and sodium thiosulfate
(McCandless et al., 1995). These films were similar to those deposited by vac-
uum evaporation, respond similarly to air heat treatments, and can be used in
the fabrication of CdTe/CdS solar cells with efficiencies comparable to those
made with evaporated CdS. Electrodeposition provides a fabrication method
using a low temperature (85OC), very low deposition current densities, and
high utilization of constituent materials.
ZnO has been of interest as a transparent n-type window in solar cells.
ZnO films of good quality have been prepared by cathodic electrodeposition
from aqueous solutions at low deposition temperatures ( 5 80°C) (Peulon and
Lincot, 1995, 1996). These films have high transparency in the visible corre-
sponding to a band gap of about 3.4 eV, and high n-type doping is possible.
The structure of the films can be varied by control of the deposition conditions
from dense films to open-structured layers of columnar crystals.
Sputtering ( S T )
The optical and electrical properties of indium-tin oxide (ITO) sputtered on
glass have been investigated to determine the conditions for maximum conduc-
tivity and transmissivity (Haines and Bube, 1978).
When an ITO/CdTe junction is formed by rf sputtering of the I T 0 onto
single crystal CdTe, a 1-pm thick surface layer of the p t y p e CdTe is converted
to n-type as a consequence of the changes in the defect structure induced by
ion bombardment and temperature, producing a buried homojunction of the
type n-ITO/n-CdTelpCdTe with solar efficiencies up to 8% and & = 0.82 V
(Courreges et al., 1980). A proposed energy band diagram is given in Fig. 5.25.
Unfortunately the n-CdTe layer is unstable and shows degradation in pho-
tovoltaic parameters as the homojunction is converted to a heterojunction
at room temperature. Related investigation of the properties of In/CdTe
n+ - IT0 n -CdTe p-CdTe

VACUUM
LEVEL
x = 4.28eV
r
I .....
,
a = 4.5eV
I
E,= 1 . W V
E f l
VB
Fig. 5.25. Proposed energy-band diagram for an ITO/CdTe junction produced by rf sput-
tering of I T 0 onto the surface of a p t y p e CdTe:P crystal, showing the n-type CdTe layer
formed by thermal effects during sputtering. (Reprinted with permission from F. G. Cour-
reges et al., J . A p p l . Phys. 51,2175 (1980). Copyright 1980 American Institute of Physics.)
junctions indicated that an approximation to a normal Schottky barrier is

obtained by vacuum evaporation of In onto an MB-etched CdTe surface, but
that for evaporated In onto a sputter-etched surface or by sputtering In onto
an MB-etched surface, the In is only a contact to a CdTe homojunction formed
by the sputtering process.
It has been shown that rf planar magnetron sputtering of both CdS and
CdTe can produce CdS/CdTe solar cells on soda-lime glass with efficiencies
above 10% (Compaan et al., 1993). The influence of substrate temperature,
rf power, target erosion, and magnetic field configuration on rf sputtering of
CdTe and CdS has been investigated (Compaan et al., 1994). The effect of
microstructure in rf sputtered CdS/CdTe cells (Shao et al., 1966), and of in-
terdiffusion of CdS and CdTe layers in laser-ablation-deposited and sputtered
cells (Fischer et al., 1996), have also been discussed.
C a d m i u m Telluride and Other 11-VI Materials 179
All high efficiency Cu(In,Ga)Sen/CdS/ZnO solar cells have been fabricated

using sputtered ZnO as the front contact. The standard two layer rf-sputtered
process from ceramic targets consists of a highly resistive pure ZnO layer fol-
lowed by an Al-doped ZnO. The role of the highly resistive ZnO layer deposited
on top of the chemical-bath-deposited CdS buffer layer, and possible influences
of sputtering pressure and 0 2 addition to the Ar sputtering gas have been in-
vestigated (Ruckh et al., 1996). A high rate reactive DC-magnetron sputtering
process of metallic Zn + A1 targets without additional substrate heating was
also developed, by which suitable ZnO layers can be prepared in less than
5 minutes. All cell parameters are essentially the same for rf-sputtered and
DC-magnetron reactive sputtered ZnO.
Chemical Bath Deposition

CdS films have been a key window layer in several of the leading solar cell
systems, including InP (see Chapter 4), CdTe, and CuInSe2 (see Chapter 6).
Several different techniques have been described for the deposition of CdS
films in CdS/CdTe cells in the above sections of this chapter. Another method
of interest for all of these applications, not specifically discussed before this,
is the method known as chemical bath deposition (CBD). In this section we
summarize the principal work in this area and the application to the different
solar cell systems described in Chapters 4,5 and 6.
CBD resembles CVD by being based on the reaction between precursor
materials in a metastable situation, but in CBD this occurs in a liquid phase
rather than in the vapor phase as in CVD. It also has some relationship to spray
pyrolysis, except that in CBD films are formed by precipitation from solution
rather than by being sprayed onto a hot substrate. CdS is usually formed from
the reaction between dissolved cadmium ions (e.g. cadmium tetrammine com-
plex ions), and thiourea molecules, in ammonia solutions (Lincot and Ortega-
Borges, 1992; Ortega-Borges and Lincot, 1993). It is a technique that allows
the formation of films near room temperature and that is adaptable to large
area processing at low Gost. Historically it began with the fabrication of PbS
photoconductive detectors (Kicinski, 1948) for which it was the principal fab-
rication technique for many years, and it has been used to prepare thin films of
a variety of chalcogenides and in the fabrication of high-efficiency CdS/CdTe
(Turner et al., 1991) and CdS/CuInSeZ solar cells (Birkmire et al., 1989; Mauch
et al., 1991a, 1991b).
Electrochemical impedance spectroscopy and quartz crystal microbalance
techniques have been applied to characterize films of CdS prepared by CBD
(Lincot and Vedel, 1991; Lincot and Ortega-Borges, 1992; Ortega-Borges and
Lincot, 1993). They conclude that film growth proceeds in two consecutive
steps, the formation of a dense compact inner layer followed by the formation
of a porous less adherent layer. A simple columnar growth model is shown
to account reasonably well for the experimental results. CBD allows the de-
position of very thin films of the order of a few nanometers in the presence
of excess thiourea, a possibility that can be quite important in seeking high-
efficiency solar cells with CdS window layers. The process has been studied
further through the use of high-resolution transmission electron microscopy,
which indicates that the growth in CdS probably proceeds by way of an atomic
mechanism, rather than by cluster coagulation as is indicated for CBD growth
of ZnS and CdSe (Lincot et al., 1993; Froment et al., 1995). The growth of
CBD CdS thin films on SnO2 and glass substrates has been analyzed using
atomic force microscopy (AFM) (Moutinho e t al., 1996). CBD CdS films have
been optically and electrically characterized (Ozsan e t al., 1994). The band
gap of these films depends strongly on the deposition conditions, increasing
with an increase in deposition rate. The films are all n-type with doping den-
sities aground 1017 cmP3 under illumination without intentional doping in the
bath.
CBD CdS films have been recently investigated in the formation of CdS/
InP, CdS/CdTe, and CdS/CuInSea junctions. Epitaxial growth of hex-CdS on
(111)*InP single crystals has been achieved using CBD from cadmium amm-
onia-thiourea aqueous solutions (Lincot et al., 1994; Froment et al., 1995), and
a solar cell based on a p I n P single crystal with InP/CBD-CdS/In203 structure
gave an efficiency of 17.8% (Saito et al., 1994). Epitaxial growth of cub-CdS on
(100) InP was achieved by CBD, probably because of lattice matching between
the CdS (100) plane and the InP (100) plane (Cortes et al., 1996).
The interaction between CBD deposited CdS films and subsequently elec-
trodeposited CdTe films in the formation of CdS/CdTe junctions has been
investigated (Ozsan et al., 1995). Results indicated that the as-deposited cub-
CdS CBD films with small grain size and high density of defects are beneficial
for the recrystallization in the cell structure during the subsequent heat treat-
ment.
CBD CdS films were successfully used in the fabrication of ZnO/CdS/
CuInSe2 solar cells, where it was found that the final cell performance depends
on the specific Cd-salt used in the CBD CdS film deposition process: High
efficiency was obtained for CdIB and CdS04 (Mauch et al., 1991a,b). Further
investigation indicated that the CBD reaction is not limited to the abrupt de-
position of a CdS layer on CuInSez, but involves chemical modifications at the
interface, with the formation of a CuInSe2/CdIn,Sey/CdS gradual structure

(Lincot et al., 1992), much like the CdSI-,Te, structure in CdS/CdTe junc-
tions described in Sec. 5.4. This solid solution formation has the beneficial
effects of removing superficial oxides, eliminating Cu,Se conducting phases in
excess, and forming a graded interface structure. Nucleation and growth of the
CdS layer on Cu(InGa)Se;? thin films is described by Friedlmeier et al. (1996).
The effect of impurities in CBD CdS films for use in Cu(In,Ga)Se;? solar
cells has been investigated by Kylner et al. (1996) using secondary ion mass
spectroscopy, Fourier transform infrared spectroscopy, Rutherford backscat-
tering spectrometry, and x-ray photoelectron spectroscopy. As-deposited films
were subjected to air annealing between 200°C and 350"C, and storage for
1.5 months in different environments. These films were found to contain 0
(primarily in CdCO3 and HzO), C, N (CN bonds), and H beside the CdS
matrix. Impurities were distributed uniformly and did not depend on the
substrate material. The CN bonds were investigated further (Kylner et al.,
1997a), who found that a high degree of disorder exists around the CN bond
in as-deposited CBD CdS films, and that the CN impurity is water-soluble
and is effectively reduced by water a t 60°C. The solar cells involving these
CBD CdS films had efficiencies greater than 15%, but correlation between CN
density and cell efficiency has not been determined. To investigate these im-
purity effects further, CBD CdS films were deposited with varying thiourea
concentrations (Kylner et al., 1997b). Both impurity content and deposition
rate are increased with increasing thiourea concentration. CBD CdS films with
thiourea concentration greater than 0.03 M showed a higher degree of disorder,
a mixture of hexagonal and cubic phases, compressive stresses in the films, and
about 0.1 eV higher optical bandgap. Photoconductivity measurements indi-
cated that the CBD CdS film with the highest amount of impurities (thiourea
concentration of 0.1 M) had the shortest photodecay time of all investigated
films. The effects associated with higher thiourea concentrations, however, do
not seem to affect the solar cell efficiency.
ZnS has a large band gap of 3.6 eV and can be used as a window layer
in thin film heterojunction solar cells (Dona and Herrero, 1994). Chemical
bath deposition has been shown to be a way to obtain adherent, specular, ho-
mogeneous and stoichiometric ZnS thin films from thioacetamide-based baths
(Ortega Borges et al., 1992; Mokili et al., 1995).
5.11. CdTe Alloys

Interest in alloys related to CdTe include research on ZnTe and Hgl-,Zn,Te
using deposition by MOCVD (Chu et al., 1989), Zn,Cdl-,Te using deposition
by CSVT (Peters et al., 1988a,b) and by MBE (Rohatgi et al., 1988, 1989),
ZnSel-,Te, using LPE (Koval et al., 1991), and Cdl-,Mn,Te using deposition
by MOCVD (Nouhi et al., 1989; Rohatgi et al., 1988, 1989).
Zn,Cdl-,Te films with Zn concentrations as high as x = 0.45 were de-
posited onto graphite substrates using CSVT (Peters et al., 1988a). Values of
x in the deposited films equal to that in the source could be achieved either
by deposition with a small temperature difference (2-8°C) between source and
substrate at atmospheric pressure of an ambient gas, or by deposition at low
ambient pressures (0.3 Torr) with any desired temperature difference between
source and substrate. For films deposited at a substrate temperature of 610°C,
p = 5 x 1015 cmP3 as determined from capacitance versus voltage measure-
ments on In/ZnCdTe Schottky barriers. No change in this hole density was
found with variations in Zn concentration.
A series of CdS/Zn,Cdl-,Te heterojunctions were prepared by vacuum
evaporation of CdS onto single crystal p t y p e Zn,Cdl-,Te substrates with
x = 0, 0.1, and 0.3 (Peters et al., 1988b). These junctions showed a max-
imum q5,, when the Zn,Cdl-,Te surface was made stoichiometric by heat
treatment in Hz before CdS deposition, a maximum q5,, for any value of x
for CdS deposition conditions yielding approximately equal carrier densities
in CdS and Zn,Cdl-,Te, and an increase in J, with increasing x. The best
junction for x = 0.3 had a q5,, of only 0.36 V. The junction transport process
resulting in relatively high values of J , (2.6 x A/cm2 in the best cell with
x = 0.3), could be modeled by thermally assisted tunneling of holes from the
Zno.3Cdo.i.Te to the interface of the junction followed by recombination there
with electrons from the CdS, provided that a high density of interface states
was assumed. It was suggested that the large values of J , were associated with
lattice distortions resulting from the solid solution formation.
Thin films of Hg,Znl-,Te over the range from 5 = 0 t o x = 0.4 have
been deposited by electrodeposition (Thero and Singh, 1996). These films
show optical absorption coefficients of the order of lo4 cm-', indicating their
possible suitability for use as absorber materials in thin film solar cells.
The processing steps involving TCJF, described in Sec. 5.4, necessary for
a solar cell involving electrodeposited HgCdTe have been discussed (Basol and
Tseng, 1986; Basol, 1988). A completed CdS/Hgo.lCdo.gTe cell was charac-
terized by q5,, = 0.62 V, J,, = 27.03 mA/cm2, f f = 0.63 and efficiency =
10.6%. Compared to a similarly electrodeposited CdS/CdTe cell (band gap of
CdTe = 1.47 eV, compared to that of Hgo.lCdo.gTe = 1.30 eV) with the same
efficiency, the CdS/HgCdTe device shows a 27% larger J,, and a 14% smaller
4oc.
5.12. Other 11-VI Junctions

Photovoltaic properties of some 50 heterojunctions formed by CSVT in the
form of five different 11-VI heterojunctions were investigated by Buch et al.
(1976, 1977). These included n-CdSelpZnTe, n-CdSelp-CdTe, n-ZnSelp-
CdTe, pZnTe/n-ZnSe, and n-CdTelp-ZnTe. Single-crystal and polycrystalline
ZnTe, single-crystal CdTe, and polycrystalline ZnSe substrates were used. Un-
der CSVT conditions, at temperatures of 375°C and above, several of the
11-VI heterojunctions involving four different atoms showed signs of alloying
and third phase formation at the heterointerface, as shown in Fig. 5.26. Val-
ues of the reverse saturation current J , were several orders of magnitude larger
than that expected for a simple recombination process for all the junctions,
suggesting the importance of recombination a t the interface.
4 Ix (Relative scale)
1.0
0.1
0.1
0.4
0.2
0
1.4 1.1 1.1 2.0 2.2 2.4 2.1 2.1 3.0 3.2
hv ( e V )
Fig. 5.26. Short-circuit spectral response curves for four 11-VI compound solar cells prepared
by CSVT. Both M-1 and M-21 are n-ZnSelpCdTe cells, but their spectral responses are
quite different. The response of M-1 resembles that of n-CdSelpCdTe cell N-3, suggesting
CdSe formation at the junction in M-1. The low-energy spectral cutoff for M-21 resembles
that of pZnTe/n-ZnSe cell P4, suggesting that in this case ZnTe is formed at the junction.
(Reprinted with permission from F. Buch e t al., J . A p p l . Phys. 48, 1596 (1977). Copyright
1977 American Institute of Physics.)
CHAPTER 6
COPPER INDIUM DISELENIDE AND

OTHER I-111-VI MATERIALS
CuGoS2 - - Cd Sipz
- Z n Si Pz
Ag I n s 2
A9 GOS C p
-- + L n SnAsZ
CUGOSCZ - CdGrb
-2n S n P2
AqGoTe2 -
A9 I n Sa2- - -
-eC d Sn Pz
CU GoTe2-
Co n e2-
-- Y! n Gc A s
$?
A9 n e2=
CuInTc2
=-1.0-
- Z n SnAs2
Fig. 6.1. Lowest energy gaps of I-111-VI2 and II-IV-V2 semiconductors in the range of
interest for solar photovoltaic conversion (Reprinted from S. Wagner and P. M. Bridenbaugh,
J. Crystal Growth 39,151 (1977) with kind permission of Elsevier Science - NL, Sara Bur-
gerhartstraat 25, 1055 KV Amsterdam, The Netherlands. Copyright 1977 Elsevier Science.)
184
Copper Indium Diselenide and Other I-III-VI Materials 185
Such a ternary compound represents the first step to more complicated solid
solutions with more than three different atoms, so that both the desired band
gap and the proper heterojunction lattice match could in principle be obtained
to provide maximum efficiency. Research on quaternary and pentenary systems
has been undertaken (Antypas and Moon, 1974; Loferski e t al., 1981) but to
date these much more complex materials have not met the stringent demands of
reproducibility and operating lifetime required for a solar cell material. Some
twenty-three ternary compounds of type I-111-VI2 and 11-1v-V~ with band
gaps in the range of interest for solar cells are summarized in Fig. 6.1.
In 1974 it was shown that a solar cell efficiency of 12010, a high value for
cells of any type at that date, could be obtained with a CdS/CuInSe2 het-
erojunction made by vacuum evaporation of CdS onto single crystal p t y p e
CuInSea, previously Se-annealed to increase its p t y p e conductivity (Wagner
et al., 1974; Shay et al., 1975).
Fig. 6.2. Current versus voltage curves under illumination by 100 mW cmP2 by tungsten-
halogen for early solar cells: all-thin-film heterojunctions of CdSjCuInSe2 and CdS/CuInSz,
and all-thin-film homojunctions of CuInSez and CuInS2. (Reprinted with permission from
L. L. Kazmerski, Univ. of Maine, Orono, Second Quarter Report t o NSF-RANN and ERDA,
NSF/AER 75-19576/PR/77/2, p. 13 (1977).)
These promising initial results led to a search for methods of preparing

thin-film CuInSe2 cells with equal or better solar efficiencies. All thin-film
CdS/CuInSez cells prepared by vacuum evaporation were fabricated with an
efficiency of 6.6%, and similar all-thin-film CdS/CuInSz cells were fabricated
with an efficiency of 3.2% (Kazmerski et al., 1975, 1976; Kazmerski, 1977). All-
thin-film homojunctions of CuInS2 and CuInSe2 were also prepared by varying
the flux of S or Se during vacuum evaporation (Kazmerski and Sanborn, 1977).
Efficiencies for the homojunctions were in the range of 3-4010. Interesting sum-
maries of the properties of these early heterojunction and homojunction thin-
film cells are given in Fig. 6.2 that compares their current-voltage curves in the
light, and Fig. 6.3 that compares their spectral response of quantum efficiency.
A step forward was marked next by the announcement of the vacuum-
evaporation preparation, using a three-source method, of all-thin-film CdS/
CuInSe2 heterojunctions with an efficiency of lo%, approaching that of the
Fig. 6.3. Spectral response of quantum efficiency for early solar cells: all-thin-film hetero-
junctions of CdS/CuInSez and CdS/CuInS2, and all-thin-film homojunctions of CuInSe2
and CuInS2. (Reprinted with permission from L. L. Kazmerski, Univ. of Maine, Orono,
Second Quarter Report t o NSF-RANN and ERDA, NSF/AER 75-19576/PR/77/2, p. 16
(1977).)
initial single-crystal device, achieved primarily by a major increase in the short-

circuit current to 39 mA/cm2 (Mickelsen and Chen, 1981, 1982). Because of its
smaller band gap, CuInSe2 cells give a higher short,-circuit current than other
high-efficiency solar cells, but a lower open-circuit voltage (40c= 0.40 V in this
case). It is noteworthy that a quantum efficiency of about 0.9 was achieved in
a film with a grain size of only about 1 pm, indicating that grain boundary
recombination is not important in CuInSez films.
Kazmerski and Wagner (1985), Bube (1987), and Zweibel and Barnett
(1993) summarize the properties of a number of solar cells involving thin-film
2-3pm
/k AI grid contact
In doped CdS or CdZnS

CdS or
0.5-lpm CdZnS
High resistivity
- 1.2pm CulnSe2
- 2.4pm Low resistivity

CulnSe7
Glass. alumina. a r
foil substrate
Fig. 6.4. Solar cell structure for a 9.6% large area CuInSez solar cell. At 1 sun, = 0.43 V,
.Isc= 35.3 mA/cm2, and fill factor = 0.63. (Reprinted with permission from W. E. Devaney
and R. A. Mickelsen, Solar Cells 24, 19 (1988). Copyright 1988, Elsevier Sequoia S.A.,
Lausanne, Switzerland.)
Fig. 6.5. Solar cell structure for the A R C 0 (now Siemens) ZnO/CdS/CuInSez solar cell. For
simulated sunlight of 100 mW/cm2, &, = 0.36-0.42 V, J,, = 35-40 mA/cm2, ff = 0.5-
0.65, and cell efficiency = 7-9%. (Reprinted with permission from J. B. Yoo, et al., J . Appl.
Phys. 68, 4694 (1990). Copyright 1990 American Institute of Physics.)
CuInSez as the absorbing material. Table 6.1 provides data and references for
specific solar cell parameters as of 1987. A reported CdS/CuInTea cell showed
no photovoltaic effect.
Overall better performance in CdS/CuInSez cells was achieved using the
backwall configuration shown in Figs. 6.4 and 6.5. Three reasons were ad-
vanced for this: (1) the lower deposition temperature for CdS as compared to
CuInSe2 minimizes diffusion between the two materials, (2) the CdS or CdZnS
window layer protects the CuInSez absorber layer from interaction with the
surface environment, and (3) a heat treatment in oxygen that proves critical
for optimizing cell performance is effective only if the CdS or CdZnS is on top.
Table 6.1. Polycrystalline Thin-Film CuInSe2-based Solar Cells (1987)
Cell Open-Circuit Short-circuit Efficiency Reference

Voltage, V Current, %
mA/cm2
A. H i g h Efficiency CuInSe2 Cells

ZnCdS/CuInSez 0.44 39.4 11.9 Devaney et al., 1985
(1 cm2) Mickelsen and Chen,
1986
ZnCdS/CuInSe2 0.43 35.3 9.6 Stanbery et al., 1984
(4 cells; 91 cm2) Mickelsen et al., 1987
ZnO/CdS/CuInSez 0.49 36.7 12.5 Potter et al., 1985
B. Experimental CuInSe2 Cells

ZnO/ZnSe/CuInSez 0.42 37 8.5 Stirn and Nouhi, 1986
Nouhi and Stirn, 1986
Nouhi et al., 1987
CdS/CuInSez 0.31 36 5.2 Thornton et al.,
(sputtered) 1984, 1987
Lommasson et al.,
1987
CdS/CuInSez 0.30 30 4.0 Shih and Qiu, 1987
(electrodeposited) Pern et al., 1987
C. CuInl-,Ga,Se2 Cells
ZnCdS/ 0.51 30.4 10.2 Chen et al., 1987
CuIno.77Gao.z3Sez
ZnCdS/CuGaSe2 0.85 11.6 5.8 Dimmler et al., 1987
ZnCdS/ 0.52 15.6 2.9 Dimmler et al., 1987
CuIn0.44Gao.56Sez
CdS/CuGaSez 0.58 9.6 2.6 Noufi et al., 1986
k
z
w
u
a
w
n
G
u
z
w
0
u.
u.
w
Fig. 6.6. NREL solar cell efficiency a s a function of year for all thin-film CuInSe2 cells.
(Data from R. F. Service 1996.)
The increase in efficiency of all thin-film CuInSea solar cells over the years
up to the present is shown in Fig. 6.6. Reviews of the progress have been given
by Meakin (1985), Rockett and Birkmire (1991), Basol (1992), and Tarrant
and Gay (1995). By 1996, several improvements developed over the intervening
years, including increasing the crystallite size by varying the concentration of
copper as the film is deposited with a copper-rich layer a t the bottom, and the
inclusion of Ga to make a larger band gap CuInl-,Ga,Sez (CIGS) material
graded with larger values of z near the bottom of the film to aid in electron
collection, have led to a 0.4 cm2 cell with an efficiency of 17.7% (J. Tuttle
et al., 1996), marking the high point on Fig. 6.6. At the same time a CIGS
cell with 100 times larger area has shown a n efficiency of 13.9% (Schock et al.,
1996).
6.2. Materials Properties of CuInSea

CuInSez has a number of properties that make it particularly suitable for use
as a solar-cell absorber material: (1) a band gap of 1.04 eV, which enables it
to absorb a large fraction of the solar spectrum; (2) a direct band gap, which
minimizes the requirements for minority carrier diffusion length, since carriers
are photoexcited close to the collecting junction; (3) the possibility of being
prepared in either n- or p t y p e form; (4) an electron affinity such that harmful
band gap spikes are not expected upon heterojunction formation with CdS,
ZnCdS or ITO; ( 5 ) a lattice constant that matches well with CdS or ZnCdS,
e.g., there is only a 1.2% lattice mismatch between the chalcopyrite structure of
CuInSez and the wurtzite structure of CdS; (6) the highest absorption constant
(3-6 x lo5 cm-') reported for any semiconductor (see Fig. 6.7);( 7 ) the ability
to be fabricated in thin-film form by a variety of techniques, as was the case
for CdTe as described in Chapter 5; and (8) excellent stability under operating
conditions (Mickelsen et al., 1982; Hsiao et al., 1983).
0.96 0.98 1.0 1.2 1.4 1.6 1.8

hU (eV)
Fig. 6.7. Dependence of absorption coefficient a on photon energy for CuInSez: (a) single
crystal, 300 K, (b) single crystal, 100 K, and (c) thin film, 300 K. (Reprinted with permission
from L. L. Kazmerski et al., J . Vac. Sci. Technol. Al, 395 (1983). Copyright 1983,
Crystal Structure
CuInSez crystallizes in a diamondlike lattice with a face-centered tetragonal
unit cell (Parkes et al., 1973). The lattice structure and unit cell for the
chalcopyrite structure are shown in Fig. 6.8. Each selenium atom serves as the
center of a tetrahedron of two Cu and two In atoms, and each metallic atom
is surrounded by a tetrahedron of selenium atoms. The lattice parameters
are a = 0.5784 nm, and c = 1.1614 nm. CuInSz and CuInTez have similar
structures.
Fig. 6.8. Chalcopyrite unit cell for CuInSez. ( 0 ) Cu, (a)

In, (0)Se. (Reprinted with permis-
sion from L. Kazmerski and S. Wagner, in Current Topics in Photovoltaics, ed. T. J. Coutts
and J. D. Meakin, Academic Press, London, p. 41 (1985). Copyright 1985, Academic Press,
London.)
Crystal Defects
The electrical conductivity of CuInSez is apparently largely determined by na-
tive defects with a high degree of compensation between defect donors and
acceptors, and can therefore be varied by the ratio Cu/In used in material fab-
rication by vacuum evaporation and by the pressure of Se used during growth
or annealing.
Neumann (1983) considered vacancies, interstitials and antisite defects in
the cation lattice as possible sources of electrically active defects, and predicted
that the active defects in p t y p e material are an indium vacancy (K,) and a Cu
antisite defect (CUI,,). In order to achieve low-resistivity, p t y p e CuInSe2, the
Cu/In ratio must be slightly larger than required for stoichiometric material.
Photoluminescence (Abou-Elfotouh et al., 1984) and cathodoluminescence
data (Masse and Redjai, 1984) were interpreted to indicate the following energy
levels for various defects; in Cu-rich material: acceptor CUI, (30 meV above
the valence band edge, V B ) ,acceptor V,, (85 meV above VB) and acceptor VS,
(130 meV above V B ) ,and in In-rich material: acceptor VC, (45 meV above
V B ) ,acceptor Vs, (130 meV above V B ) and donor Inc, (35 meV below the
conduction band edge).
Masse (1990) reviewed the various energy levels of defects with a low energy
of formation, reported for I-111-V12 compounds (e.g. for CuInSe2: Vs,, Vc,,
V,,, and C U ~ , ) ,and concluded that evidence favors a hydrogenic acceptor
associated with a VC, rather than an antisite defect.
Hole and electron traps have been investigated using Deep Level Transient
Spectroscopy (DLTS) in single crystal Schottky junctions based on CuInSe2
(Igalson and Bacewicz, 1994) and in thin film CuInSe2/CdS/ZnO photovoltaic
devices (Igalson and Schock, 1996). The general effect observed is a decrease in
the density of shallow electron traps and an increase in the density of hole traps
after an injection of electrons, metastable below 200 K. It has been proposed
(Igalson, 1993) that this phenomenon can be described appropriately in terms
of a model involving two charge states of the same defect, similar in many ways
to the behavior of the dangling-bond defect in a-Si:H discussed in Chapter 3.
The data suggest that electron traps are converted to hole traps after the
capture of two electrons, and a possible candidate for the defect is a double
donor In/Cu or a complex related to it. Similar indications of metastable defect
behavior in Cu(In,Ga)Sea cells have been reported (Schmitt et al., 1996; Walter
et al., 1996a), and in CuIn(SSe)z films (Herberholz et al., 1996).
A method to deduce energy distributions of defects in the band gap by
measuring the complex admittance of a junction has been applied to hetero-
junctions of pCu(In,Ga)Sea thin films with n-ZnO (Walter et al., 1996b). A
distribution of hole traps with maximum density corresponding to an ioniza-
tion energy of about 0.3 eV was indicated, similar to the results of modulated
photoconductivity (Herberholz et al., 1994) and DLTS measurements (Igalson
and Bacewicz, 1992).
Minority Carrier Diffusion Length

The high ionized acceptor density in pCuInSe2 does not seem to cause a large
decrease in the minority carrier diffusion length. Diffusion length values of
0.5 pm from the photoelectromagnetic effect (Mora and Romeo, 1977), 2.5 pm
from EBIC data on pCuInSe2/CdS heterojunctions (Piekoszewski et al., 1980),
and 1.0 pm from surface photovoltage measured with pCuInSe2/electrolyte
diodes (Johnson et al., 1985), have been reported.
Optical Absorption
Figure 6.7 shows the high values of absorption constant achieved with CuInSe2
which correlate with the high values of J,, found in solar cells based on
CuInSez. Figure 6.9 shows the variation of absorption with photon energy
for single crystal and thin film CuInSe2, indicative of a direct band gap with
magnitude EG for which it would be expected that (cuhv)2 would be propor-
tional to (hv- EG). Differences between the single crystal and thin film curves
in Fig. 6.9 are probably due to small differences in composition.
Fig. 6.9. Dependence of optical absorption of CuInSe2 on photon energy plotted as (ahv)2
versus photon energy hv, which yields a linear relationship for a direct band gap. (m) single
crystal at 300 K, ( 0 ) thin film at 300 K, ( 0 ) thin film at 100 K, and (A) annealed thin film
at 300 K. (Reprinted with permission from L. L. Kazmerski et al., J. Vac. Sci. Technol.
A l , 395 (1983). Copyright 1983, American Institute of Physics.)
The absorption edge of CuInSe2 is shifted to higher energies with increasing

In content. For In/(Cu +
In) < 0.65, the band gap of the stoichiometric
CuInSe2 at about 1 eV is still detected. It has been suggested that for 0.50 <
+
In/(Cu In) < 0.66, the material is composed of two parallel existing phases,
both CuInSe2 and the ordered defect compound CuIn2Se3.5 (Schaeffler and
Schock, 1995).
Interface Properties
In Sec. 5.4 the importance of interface interactions in the CdS/CdTe het-
erojunction structure leading to the formation of CdTel-,S, were described.
Similar investigation has been made of the possible reactions between different
species a t the CdS/CuInSez interface. Analyses involving x-ray photon spec-
troscopy (XPS) (Kazmerski et al., 1982) and electron energy loss spectroscopy
(EELS) (Jamjoum et al., 1982) both indicate the presence of a chemical reac-
tion at the CdS-CuInSez interface with the formation of CuzS and Cu2Se as
the reaction products.
Oxidation of CuInSe2
Oxidation studies have been made both on p t y p e polycrystalline thin films fab-
ricated by three-source deposition, and on Bridgman grown crystals (Kazmer-
ski et al., 1981, 1983a). For single crystals oxidized at 140°C XPS shows
the formation of Cu,Se at the dry oxide/CuInSe2 interface. The native ox-
ide formed on a (110) cleaved CuInSez surface by simple exposure to dry
air at room temperature is primarily In203 with less than 5% SeO2. If the
oxidation is thermally induced using either dry oxygen or dry air, the frac-
tion of SeO2 is approximately doubled, and evidence for Cu,Se is seen a t the
interface. For anodic oxidation (exposure to electrolyte solution of sodium
tartrate/HzO/tartaric acid, pH = 6.0 a t room temperature), the fraction of
In203 is reduced and evidence is found for about 10% CuzO, 10% CuO, and
2% Se are found, with CuO at the interface. For CdS/CuInSez cells, a heat
treatment at 200-220°C in oxygen or air consistently improves the operating
characteristics, as illustrated in Fig. 6.10, while heating in high vacuum, Ar,
N, H, or He does not seem to degrade the cell performance.
Non-ideal current-voltage characteristics of thin film CuInSe2 solar cells
such as cross-over of the dark and light current-voltage curves, or strongly
bias dependent current collections, have been attributed to surface oxidation
occurring during several processing steps (Walter et al., 1995). These include
Copper I n d i u m Diselenide and Other I-111-VI Materials 195
I I I I
a2 0.4
Voltage IVI
Fig. 6.10. Effect of heat-treatment in oxygen on light and dark current-voltage characteristics
of CdS/CuInSeZ heterojunction s6lar cell. Dashed line, before 0 2 anneal; solid line, after 0 2
anneal. (Reprinted with permission from R. A. Mickelsen et al., “Cadmium Sulfide/Copper
Ternary Heterojunction Research”, final Rep. XJ-9-8021-1, Boeing Aerospace Co., Seattle,
WA (1982). Copyright 1982, Boeing Aerospace.)
the use of oxygen during the rf sputtering of the ZnO window layer, the air
exposure of the absorber prior to the deposition of the window, and the use of
an In,(OH,S), buffer layer.
Thermal Stability
Low-temperature annealing of the CdS/CuInSez solar cell does not alter its
electrical or interface composition (Kazmerski et al., 1982; Kazmerski, 1983;
Mickelsen and Chen, 1983; Hsiao et al., 1983). Annealing a t 60°C for 7500
hours causes no changes in cell performance or in the compositional appearance
of the interface. Changes do begin to occur when the temperature is raised
above 200°C. Two hours of annealing in Ar at 220°C caused decreases in &,
of 5%, J,, of 17%, f f of 21%, and efficiency of 38%; these results suggest that
the heat treatment has caused growth of the interfacial transition layer, and
XPS identifies the existence of Cu,S and Cu,Se at this interface (Wager et al.,
1983). Heat treatment above 400°C causes a catastrophic degradation of solar
cell performance due to the rapid diffusion of Cd across the interface region,
an effect that is more severe in polycrystalline thin-film cells than in single
crystal cells, suggesting that grain-boundary diffusion is involved.
Contacts
A basic characteristic of almost all CuInSe2 solar cells is the Mo back con-
tact. Often high-efficiency solar cells show a non-ohmic contact behavior that
has been attributed to the Mo/CuInSea back contact. Earlier measurements
indicated that the nature of the Mo contact to single crystal CuInSez de-
pended on the defect density in the CuInSez (Abou-Elfotouh et al., 1989).
The current-voltage characteristics of the Mo/CuInSez contact on operating
solar cells prepared by selenization of Cu/In precursors in H2Se with the Mo
deposited by sputtering, the CdS by chemical bath deposition, and the ZnO by
rf sputtering, were measured by a technique that allowed separate evaluation
of the contact properties and showed the Mo contact to be completely ohmic
(Shafarman and Phillips, 1996). Simulations suggest that the CdS/CuInSez
interface is the most likely origin of the non-linear current-voltage effects.
6.3. Fabrication Techniques

A variety of techniques has been used for film and crystal growth of CuInSe2,
and fabrication of solar cells. These are summarized, with appropriate refer-
ences, by Kazmerski and Wagner (1985). The materials requirements for the
CuInSez technology have also been reviewed by Birkmire et al. (1984).
Single- Crystal Growth

Methods used for single-crystal growth include (a) direct growth from ele-
mental constituents by cooling a stoichiometric melt, zone-melting, horizontal
directional solidification, and Bridgman growth (which has produced device
quality p t y p e crystals - Bachmann 1983); (b) direct growth, not from the
elemental constituents, but from binary compounds such as CuzSe + InzSe3,
which enables the use of lower pressures in the growth ampoule; (c) chemical va-
por transport, typically using iodine as the carrier for the ternary constituents;
and (d) liquid-phase epitaxy on ZnSe substrates using Bi as a solvent.
Vacuum Evaporation
Three variations of vacuum evaporation have been used for the deposition
of CuInSez films. (1) Single-source deposition or flash-evaporation uses a
Copper I n d i u m Diselenide and Other I-Ill-VI Materials 197
single-phase powder as the source. Single-source deposition has not been

particularly successful for CuInSe2 since it often results in uncontrolled Se
or Cu deficiencies. Flash evaporated films also have a very small grain size
(< 100 nm). (2) Double-source deposition uses a second source of Se together
with a CuInSez source, to compensate for the loss of Se during deposition, and
has been successful in producing device quality films with grain sizes of about
2.5 pm. Still the electrical properties of the films depend critically on the de-
position parameters. (3) The greatest degree of control of the stoichiometry is
achieved with the three-source deposition method, evaporating the three con-
stituent elements independently (Mickelsen and Chen, 1981; Mickelsen et al.,
1982; Hsiao et al., 1983).
Multisource vacuum evaporation has been used to analyze the growth pro-
cess and the interactions of different phases (Klenk et al., 1993). Growth of
films has been analyzed for growth with excess Cu, CuInSe2/CuGaSe2 multi-
layers, and growth of CuIn(Se,S)a at different Cu/In ratios. It is concluded
that excess Cu provides a binary copper chalcogenide that acts as a flux with
a high diffusion coefficient for species involved in the growth process. It is not
possible to adjust the S / S e ratio or to maintain Ga/In gradients as long as the
growth is dominated by the copper chalcogenide.
Selenization of Metal Layers

A second major method for the preparation of CuInSe2 films for solar cells
is by selenization of previously deposited metallic Cu and In layers. Basol
et al. (1989) and Basol and Kapur (1990b) used electron-beam evaporation
to obtain Cu and In films deposited on a Mo-coated glass. Selenization was
carried out in an HzSe atmosphere to produce completed solar cells with an
efficiency of almost 11%. Talieh and Rockett (1989) used a hybrid process
consisting of sputtering Cu and In with evaporation of Se to produce final
cells showing efficiencies greater than 7%. Dimmler et al. (1988) compared
CuInSez films produced both by thermal evaporation of the single elements
and by selenization of the metal films and found many similarities between the
two processes.
Process details in the selenization technique using HzSe have been consid-
ered by Verma et al. (1991, 1992). Cu-In bilayers were selenized in H2Se gas
at 400°C in a tubular reactor, and results were compared with Cu-In bilayers
selenized by physical vapor deposition using Se at substrate temperatures be-
tween 150°C and 400°C. It was observed that selenization in the PVD reactor
with Se proceeded faster and at lower temperatures than in the tubular reactor
with HZSe.
High efficiency solar cells could not be made on CuInSe2 films formed in
a tubular reactor using only HzSe as the reacting gas, but by mixing 0 2 with
the HzSe, CuInSeZ was formed from which cells with efficiencies over 10% were
fabricated (Verma et al., 1993). For OZ/HzSe ratios of 0.9 to 0.2, Cu7Se4 and
In203 were formed along with the CuInSez. But for low 02/H2Se ratios, 0.02
to 0.004, single phase CuInSez films were formed suitable for photovoltaic cells.
It was suggested that the presence of oxygen in a dilute HzSe mixture stabilizes
the morphology of Cu-In films when heat treated at 400°C in Ar or Ar/H2,
controls the amount of Se, species formed in the gas phase, and causes In loss
during CuInSe2 film growth resulting in the formation of a copper selenide
phase.
Yamanaka et al. (1993) evaluated the process of selenization of Cu-In layers
with elemental Se at temperatures between 150" and 650°C. At temperatures
above 250°C it was deduced that In in the liquid phase reacts with Se to form
InSe, then reacts with CuTSe4 to form CuInSe2, which a t these temperatures
is the dominant phase in the film.
A model describing the chemical kinetics of the selenization of Cu-In layers
has been developed (Russell et al., 1994a,b)for both the tubular reactor growth
with HzSe and for a PVD selenization reactor.
A chemical modification of the Mo-coated substrate has been proposed as
a means of obtaining better quality CuInSez films (Basol et al., 1991). Use of
a Te interlayer on the Mo surface before the deposition of C u / h precursors
and subsequent selenization is reported t o produce stoichiometrically, morpho-
logically and mechanically superior CuInSe2 films. It is suggested that thin
interfacial layers of metals such as Cr and T i might also effectively improve
the adhesion of the CuInSe2 films.
An alternate sequential deposition process involves the deposition of InSe,
and Cu at a low substrate temperature followed by a high temperature sel-
enization step, resulting in an efficiency of 14% for solar cells based on these
layers (Zweigart et al., 1995, 1996).
MOCVD
An extensive investigation has been made of the use of MOCVD techniques
to deposit CuInSez thin films for solar cell applications (Sagnes et al., 1992;
Artaud et al., 1994a,b;Ouchen et al., 1995a,b). It was shown that the MOCVD
process performed in a horizontal reactor operating at atmospheric pressure,
with H2 as the carrier gas, was suitable to grow polycrystalline CuInSe2 thin
films with properties comparable to those deposited by vacuum evaporation.
Copper I n d i u m Diselenide and Other I-111-VI Materials 199
The original approach involved a single step codeposition process from three
precursors: TMIn (trimethylindium), (hfa)2 Cu NHEt2 (hexafluoroacetyl-
acetonato copper mixed with diethylamine), and H2Se. This produced ma-
terial suitable for photovoltaic conversion, but with a n efficiency below 3%.
Better results involving enhanced grain size were indicated by a multistep
deposition process using different substrate temperatures, and based on the
growth of a ternary CuInSe2 film on a starting layer of Cu(Se) or In(Se) to
provide quasi-epitaxial growth.
Sputtering
Attempts to deposit CuInSe2 films by radio frequency or magnetron sputter-
ing, a technique that is promising for large-area cell production, result in films
with grain size and reproducibility problems. Samaan et al. (1983) used rf
sputtering in argon gas using p t y p e polycrystalline CuInSe2 ingots or loose
powders as the targets, Piekoszewski et al. (1980) used water-cooled, pressed
powder targets of CuInSe2, and Thornton et al. (1984) used reactive mag-
netron sputtering by simultaneously sputtering Cu and In in an Ar +
HzSe
atmosphere to produce cells with an efficiency of 556%.
In an effort to reduce the density of defects in sputtered CuInSez films,
presumably caused by bombardment by high-energy particles from the Se tar-
get, a technique known as “hybrid sputtering” has been developed in the effort
to make the voltage applied to all targets as low as possible (Nakada et al.,
1995). In this technique, the Se target source of high-energy ions is replaced
by a Se effusion cell. Films deposited by this hybrid sputtering method show
relatively large grain size and low density of defects, enabling the fabrication
of an 11.3% efficient cell.
Spray Pyrolysis
The convenient, low-cost method of spray pyrolysis has been used t o produce
thin-film CuInSe2 by spraying a freshly prepared aqueous solution of saturated
CuC1, InC13 and N-dimethyl selenide in the ratio 4:1:0.5 onto a heated substrate
(Pamplin and Feigelson, 1979; Gorska et al., 1980). Mooney et al. (1980)
used spray pyrolysis to produce low-resistivity n-type CuInSe2 which was then
converted to p t y p e by heat-treatment in H2/H2Se at 6OO0C, and showed a
photovoltaic response in sprayed CdS/CuInSez junctions. The technique has
not yet been shown to be suitable for general solar cell applications.
Recently CuInSez/CdS heterojunction solar cells were deposited by spray

pyrolysis with a maximum efficiency of 4 5 % (Varner 1996). A Cu:In:Se ratio of
0.94:1:3.3 in solutions sprayed at 275°C produced the best results for CuInSez
films: p = 10l6 cmP3, p = 3000 ohm cm, and p = 0.2 cm2/V-sec. This mobil-
ity is about 25 times smaller than that obtained in evaporated CuInSez films.
A Cd:S:In ratio of 1:1.2:0.03 at 350°C with a CdC12 molarity of lo-' M in
solution, produced CdS films with n = 8 x 10l6 ~ m - p~ = , 40 ohm cm and
p = 3 cm2/V-sec, a mobility that is about 1/3 that of evaporated CdS films.
Both the CdS and the CuInSez layers were subjected t o a variety of analyses
including electrical resistance, thermoelectric power, x-ray diffractometry, elec-
tron microprobe, and scanning electron and optical microscopy. The relatively
low efficiency values were attributed to the small grain size of 0.1-0.2 pm in the
sprayed CuInSez. As-deposited cells showed an efficiency of about 2%, which
increased with prolonged exposure to air at room temperature, but could not
be reproduced by heat treatments in air.
Electrodeposition
Pern et al. (1987) described the preparation of CuInSea films by a one-step
electrodeposition process. The film quality was affected by the concentration
of the buffering agent ethylenediamine, which must be kept below 0.125 M to
produce photovoltaically useful films.
The phases obtained under various conditions of potential and flux ratio in
the application of electrodeposition techniques t o the preparation of CuInSe2
films have been investigated (Thouin and Vedel, 1995; Vedel et al., 1996).
It has been concluded that a combination of one-step electrodeposition and
annealing treatment in a Se atmosphere is a promising approach for improv-
ing the quality of electrodeposited CuInSez films for photovoltaic applications.
(Guillemoles et al., 1996; Lincot et al., 1994). The properties of electrode-
posited/selenized films were investigated by luminescence measurements, Hall
effect and photoelectrochemical characterization. Films are p t y p e , with carrier
densities of 10'6-10'7 cmP3, and diffusion length of about 1 pm. An efficiency
of 6.5% is reported for the best CuInSea/CdS/ZnO solar cell prepared in this
way to date. Interface recombination, not bulk properties, is shown to be the
dominant loss mechanism.
Close-Spaced Vapor Transport

The close-spaced vapor transport method (CSVT) has been applied t o the
growth of CuInSez, CuGaSe2 and Cu(Ga,In)Sez thin films (Masse and Djessas,
1993, 1994). The deposits were made on glass or Mo substrates below 620°C in
glass tubes sealed under vacuum after the introduction of solid iodine. Films
obtained above 550°C have a composition close to the stoichiometric compo-
sition. Except for low iodine concentrations (< 0.1 mg cmP3) or high iodine
concentrations (> 0.5 mg ~ m - ~ film
) , growth transport is governed by diffu-
sion.
Films deposited on SnO2 show a new photovoltaic effect with the positive
polarity on the SnO2, presumably because of the formation of a doping gradient
in the CuInSe2 films due to the deposition conditions (Masse and Djessas,
1995).
Molecular Beam Epitaxy

Nearly stoichiometric epitaxial films of CuInSeZ have been grown on GaAs
(001) by molecular beam epitaxy, and low temperature photoluminescence
measurements have been used to characterize defects involved in radiative re-
combination (Niki et al., 1994).
6.4. Solar Cell Developments

The main developments in solar cells can be described best by distinguishing
between the techniques used for film fabrication. The dominant two techniques
are three-source vacuum evaporation, and selenization of pre-deposited Cu and
In metal layers.
Fabricated by Three-Source Vacuum Evaporation

Mickelsen et al. (1987) and Devaney and Mickelsen (1988) describe the vac-
uum deposition processes successfully developed for the production of large
area, high efficiency CuInSez solar cells. In the fabrication of solar cells by
these techniques (see Fig. 6.4), a Mo base electrode is sputter-deposited, two
CuInSea layers (one of low resistivity with Cu/In ratio slightly larger than one,
and one of high resistivity with Cu/In ratio less than one) are deposited from
three elemental sources by physical vapor deposition. Only Mo can be used as
the contact metal because of the high reactivity of CuInSea at these tempera-
tures. The Zn,Cdl-,S window layer is deposited by either resistively heated
or electron-beam evaporation sources with CdS, ZnS, or ZnCdS as the starting
material. Replacement of the co-evaporation of ZnS and CdS sources by elec-
tron evaporation of a sintered Zn0.13Cd0.87Ssource material led to better com-
position uniformity. The single CdS or ZnCdS window layer was later replaced
by two layers, a lower undoped layer next to the CuInSez and an upper n-type
doped layer. Heat treatment of the deposited cell for 10-40 minutes in oxygen
at 225"C, needed to achieve optimum efficiency, apparently provides a grada-
tion in composition of the two CuInSe2 layers. Cells with areas up to 91 cm2
were prepared with an efficiency of 9.5%. These cells had the following struc-
ture: soda lime glass/2-3 pm Mo/3 pm CuInSe2/2 pm ZnCdS/Al-/SiN/SiO.
Early anti-reflection coatings of MgFZ/SiO, were replaced by plasma enhanced
chemical vapor deposition at 175°C of amorphous hydrogenated SIN and SiO
films.
Several investigations were made of the effect of the specific composition of
the CuInSe2. Noufi et al. (1984) used the three-source deposition method to
prepare a large number of films, varying the Cu/In ratio from 0.4 to 1.2 from
film to film, while keeping the In and Se rates constant. The results indicated
that the control of the electrical properties of CuInSea films, and hence the
performance of solar cells using them, required good control of stoichiometry
since the electrical properties are dominated by native defects.
Noufi and Dick (1985) examined the compositional and electrical proper-
ties of the two-layer CuInSea structure characteristic of the cells prepared by
Mickelsen et al. (1987). They found that in the final solar cell device, the
two individual CuInSe2 layers had mixed and remained p t y p e during the cell
processing steps, except for the very last few tenths of a micrometer to deposit,
which was Cu-deficient and of high resistivity; the two CdS layers consisted of
an almost stoichiometric layer close to the junction and a top In-doped low-
resistivity layer. Rocheleau e t al. (1987) investigated the tolerance of CuInSeZ
solar cells of this type to variations in film composition. They found that cell
efficiencies of 10% or better could be obtained for a range of Cu from 23% to
27% and a range of indium from 25% to 28%.
The effects and mechanisms involved in the required air-bake to optimize
these cells has been investigated. Noufi et al. (1985, 1986a) have studied the
effect. of the air-bake on the spectral response of CdS/CuInSeZ cells, alternate
methods of oxidizing or reducing the CuInSe2 (Noufi et al., 1986b), the depen-
dence of the electrical conductivity of CuInSe2 on composition and oxidation
(Datta et al., 1985), and the variation of the thermally stimulated conductivity
of CuInSe2 with oxidation (Datta et al., 1986). Their results can be summa-
rized as follows: (1) improvements in cell performance on air-baking consist
primarily of increases in open-circuit voltage and fill factor; (2) air-baking was
beneficial only if the temperature was not greater than 2OO0C, degradation
being caused by higher temperatures; (3) the effect of the air-bake was to
Copper I n d i u m Diselenide and Other I-III-VI Materials 203
introduce oxygen into the CuInSez with effects that could be duplicated by the
use of chemical oxidants or reversed by the use of chemical reducing agents such
as hydrazine or by exposure t o an electron beam; (4)the effect of oxygen in the
CuInSe2 films was to increase the p t y p e electrical conductivity, presumably
by the compensation of donors associated with interstitial In or In-on-Cu-site
defects, as suggested also by a decrease in the thermally stimulated conductiv-
ity associated with these levels, or by tying up dangling bonds at the surface
of selenium-deficient CIS grains. Damaskinos et al. (1987) showed that the re-
sistivity of the CuInSe2, which depends on its state of oxidation, is responsible
in the solar cell for large reverse saturation current, low open-circuit voltage,
and large cross-over between dark and light current versus voltage curves. All
these phenomena appeared to be reversible by oxidation/reduction cycles.
Fabricated by Selenitation of Metal Layers

Mitchell and Liu (1988) and Mitchell et al. (1988) summarize developments in
the CuInSe2 solar cell developed a t ARC0 Solar (now Siemens Solar) using an
originally proprietary method for the details of the deposition of CuInSez , later
revealed to be a two-step selenization process as described above (Love and
Choudary, 1984; Kapur et al., 1986; Ermer and Love, 1989; Eberspacher et al.,
1989). The thick ZnCdS layer is replaced by a very thin CdS layer covered
by a transparent, conducting ZnO layer (Potter et al., 1985). A typical cell
structure for a ZnO/CdS/CuInSez cell is glass/Mo/2 pm CuInSez/< 50 nm
CdS/1 pm ZnO/grid metallization, as shown in Fig. 6.5. Unlike the cells fabri-
cated by vacuum evaporation, no subsequent heat treatment is required. Like
the cells fabricated by vacuum evaporation, the Cu/In ratio in the CIS de-
termines the efficiency, and Cu/In = 0.92 to 0.97 is preferred (Zweibel and
Barnett, 1993). The use of the very thin CdS layer and the transparent ZnO
layer allow utilization of photons with wavelengths between 380 and 520 nm,
which are normally absorbed in the thick CdS layer. The ZnO has a sheet
resistance of less than 10 ohms/square, minimizing the series resistance losses.
At 25'C the measured depletion layer width of 240 nm indicates that the thin
undoped CdS is fully depleted. Single-cell efficiencies above 12% have been
achieved, a 30 x 30 cm2 module has been fabricated with a 9.7% active area ef-
ficiency, and with improved ZnO, a record short circuit current of 41.2 mA/cm2
was achieved.
Several investigations have been directed toward the exploration of the
possibility of replacing the CdS film in the ZnO/CdS/CuInSez cell with a ZnSe
film. Nouhi et al. (1988) reported that conducting ZnSe:In deposited by DC
magnetron sputtering can be used as an alternative to CdS as an intermediate

layer. In a hybrid cell of n-CdSli-CdSli-ZnSelCuInSe2, containing both a
1 pm thick conducting CdS film and a 1 pm thick insulating CdS film, as
well as a < 50 nm thick insulating ZnSe film replacing the insulating CdS film
in the ARC0 ZnO/CdS/CuInSe2 cell, it was shown (Yo0 et al., 1991) that
(1) the cells with a ZnSe intermediate layer have an increase in the diode
factor and a decrease in dark J , compared to cells wit,hout a ZnSe layer, but
(2) the cells with ZnSe do not show a n increase in qboc as was hoped, because
of a change in the junction transport mechanism under illumination, and (3)
cells with a thicker ZnSe layer ( 2 40 nm) show strong photosuppression.
Research on ZnSe or ZnO buffer layers has shown that ZnSe/CuInSez
cells can be prepared with high voltages and efficiencies of the order of 14%,
and efficient ZnO/CuInSe2 cells with graded CuInSe2 have been fabricated by
MOCVD grown ZnO films (Olsen et al., 1994, 1996). Cells with a ZnSe layer
deposited by an atomic layer deposition method produced a CuInl-,GaxSe2
thin-film solar cell with efficiency of 11.6% (Ohtake et al., 1994). Cells with a
chemical-bath-deposited ZnO buffer layer have yielded an efficiency of about
10% (Nii et al., 1994).
Other replacements for the CdS film (or “buffer-layer”) in Cu(In,Ga)
(Se,S)2 solar cells have also been proposed. Typical of these are In,(OH,S),
and Sn(O,S)2 deposited in a chemical bath process (Hariskos et al., 1995,
1996). Conversion efficiencies of 15.7% were obtained with a CBD In,(OH,S),
layer, but the device performance depended markedly on the illumination, cor-
related to light absorption in the buffer layer. Efficiencies of only 12% or less
were obtained with SnO2 or Sn(O,S)2 buffer layers, and indications are that
the absorber layer close to the heterojunction is affected by the buffer layer
deposit ion.
Additional Solar Cell Insights

Several investigations indicate that the dominant mechanism controlling the
junction current of CuInSe2 solar cells at room temperature is recombination
in the CuInSe2 (Mitchell et al., 1988; Roy et al., 1988; Turner e t al., 1988; Yo0
et al., 1989; Shafarman and Phillips, 1991).
Ruberto and Rothwarf (1987) investigated the time-dependence of the
open-circuit voltage with illumination time in CuInSez/CdS solar cells, and
proposed a process involving the tunneling of electrons trapped in deep states
in the CdS, near the junction with the CuInSe2 layer, to the CuInSe2 valence
band.
CuInSez junction structures have been analyzed by EBIC, optical beam-

induced current (OBIC) and related measurements a t room temperature
(Chesarek et al., 1988) and a t low temperatures (Noufi et al., 1988). Below
220 K a second space charge developed in the bulk of the CuInSea in addition
to the CuInSez/CdS interface, suggesting that the band diagram for the de-
vice was not that of a simple heterojunction. Minority carrier traps in CuInSez
have been detected by use of thermally stimulated capacitance spectroscopy
(Ramanathan et al., 1988).
A variety of models have been advanced t o describe the properties of the
solar cells based on CuInSez. These include a p i - n heterojunction model
(Rothwarf, 1982), a heterojunction model with the majority of the depletion
region within the CuInSez (Potter et al., 1985), and a heterojunction model
with charge on its interface (Rothwarf, 1986).
CuInSez/CdZnS/ITO solar cells prepared by different groups with differ-
ent techniques have been compared (Shafarman and Phillips, 1993). Included
were cells fabricated at the Institute of Energy Conversion (IEC) of the Uni-
versity of Delaware by evaporation, selenization with HzSe, and selenization
by Se; at Siemens Solar Industries (SSI); at Energy Photovoltaics, Inc.(EPV)
by selenization by Se; and at the Institute for Physical Electronics (IPE) at
the University of Stuttgart by evaporation. The cells were subjected to ex-
tensive current-voltage measurements over a wide range of temperatures. If
the solar cell parameter data for all six of these quite different cell fabrication
*
techniques are averaged, the strikingly similar results are & = 0.44 0.01 V,
* *
J,, = 35 2 mA/cmz, f f = 0.65 0.02, and efficiency = 10.1 0.5%. An *
analysis of the current-voltage curves shows that the basic junction mecha-
nism is the same for all the cells with a barrier height of about 1.0 eV and
a diode quality factor A of about 1.5. The different cells do show different
nonlinear series resistances, which must be taken into account when analyzing
the current-voltage data.
The role of the chemical-bath-deposited CdS layer on CuInSea and Cu
(In,Ga)Sez solar cells has been investigated to explore the origin of the “red
kink” effect in which current-voltage curves show a “kink” around the open-
circuit voltage when illuminated with red light (Hou et al., 1996). The effect is
associated with a low free electron density and a high trap density in the CdS
layer. White light enhances the free electron density in the CdS and leads t o
positive charge trapping in this layer. This trapping enhances the photocarrier
separating barrier in the absorber and improves the cell performance. Sim-
ulations of the effect are in agreement with the CuInSez cell band structure
suggested by Schmid et al. (1994).
Substrates
The commonest substrate for the CuInSez solar cell is Mo on soda-lime glass.
Effects due to Na diffusion from this glass substrate into the CuInSe2 layer
during cell fabrication by HzSe selenization have been investigated (Basol et al.,
1994). Excessive Na diffusion through the Mo layer and its reaction with the
processing atmosphere at the Mo/CuInSe2 interface may limit the efficiency
due to the formation of a high-resistivity layer near this contact. On the other
hand, a moderate level of Na diffusion through the Mo layer dopes the CuInSe2
layer p t y p e and improves the efficiency of the cells, especially those with low
Cu/In ratios.
The influence of substrates, particularly alkali free substrates versus soda
lime glass, on Cu(In,Ga)Se2 thin films has been investigated by Ruckh et al.
(199613). The presence of Na in films on soda lime glass is correlated with
an enhanced formation of S e - 0 , In-0, and Ga-0 bonds a t the surface after
several days of exposure to air, the electrical conductivity is one order of mag-
nitude higher, and solar cells prepared on these substrates exhibit increased
open-circuit voltage. Junctions prepared on alkali free substrates show an in-
creased space charge width. These results can be explained in terms of a higher
acceptor density in the films prepared on soda lime glass.
Efforts have been directed toward developing flexible substrates for CuInSez
solar cells. The first efficient CuInSez cell on a flexible metal substrate was
described by Basol et al. (1993). A selenization technique was used involving
H2Se and e-beam evaporated Cu/In precursor layers t o obtain CuInSez. Mo,
Ti, and A1 foils were evaluated as possible flexible substrate materials for solar
cells. Flexible cells (capable of being bent to a radius of curvature of about
2 cm) upon Mo foil substrates had a conversion efficiency of above 8%.
Problems associated with these metal films when large-scale module fab-
rication was considered, led to the investigation of an insulating, light-weight
and flexible polymeric substrate: a 50 pm thick KAPTON polyimide sheet
supplied by Dupont (Basol et al., 1996). The best 1 cm2 area device showed a
total area efficiency of 8.7%.
6.5. Related Alloys and Materials

Chen et al. (1987) prepared thin-film polycrystalline solar cells based on het-
erojunctions of CuGa,Inl-,Sez/ZnCdS with values of 5 between 0.1 and 1.0.
The quaternary selenide films were deposited by simultaneous elemental evapo-
ration onto a heated Mo-coated alumina substrate, using a two-layer deposition
procedure like that decribed above, and the Zno.lzCdo.88S window layer was
deposited by vacuum evaporation in a separate chamber. Anti-reflection coat-

ings of SiN and SiO were deposited by a low temperature, plasma enhanced,
chemical vapor method. The band gap for the quaternary compounds varies
from 1.0 eV for x = 0 to 1.7 eV for x = 1.0. Substitution of Ga for In causes an
increase in the open-circuit voltage, but a decrease in the short-circuit current
and a decrease in the fill factor. See Table 6.1 for typical values of the solar
cell parameters. Effects of partial substitution of Ga for In appeared to be
optimized for z = 0.23. CuGa,Inl-,Se2/ZnCdS heterojunctions fabricated by
deposition by vacuum evaporation have also been investigated by Klenk et al.
(1988), Dimmler et al. (1988) and Devaney et al. (1988, 1989).
Properties of solar cells involving Cu(1nGa)Sez films deposited on Mo-
coated glass substrates by vacuum evaporation from four elemental sources
in a vacuum chamber have also been investigated (Birkmire et al., 1995;
Shafarman et al., 1996). A simple two-step deposition process was used:
(1) depositing a Cu-rich Cu(1nGa)Sez film with the substrate heated to 450°C,
followed by (2) increasing the substrate temperature to 600°C and shutting off
the Cu flux while continuing the same In, Ga, and Se fluxes. The result is a
single phase Cu(InGa)Se:! film of homogeneous composition. Solar cells were
completed using chemical-bath deposited CdS, sputtered ZnO window layers,
evaporated Ni/Al, and MgFz anti-reflection layers. Figure 6.11 summarizes
the dependence of (a) band gap, (b) open-circuit voltage, (c) short-circuit cur-
rent, and (d) solar cell efficiency, for nine Ga/(In + Ga) ratios between 0.27
and 0.81. All the cells with Ga/(In + Ga) less than 0.5 have a n efficiency of
about 15%, decreasing to 8.8% for Ga/(In + Ga) = 0.81. The increase in open
circuit voltage is proportional to the increase in band gap, and the short-circuit
current decreases as expected with increasing band gap.
A three-stage selenization process has been used for the preparation of
CuGaInSez/CdS thin film solar cells with an efficiency greater than 15%
(Romeo et al., 1997). The three stages correspond to: (1) deposition of Cu,
In, and Ga elemental layers on Mo-covered soda lime glass and selenization in
Se vapor, (2) and (3) only Cu and Ga are used as elemental layers in order to
increase the amount of Ga in the CuGaInSez film.
The compound with composition CuInsSes, referred to as an ordered va-
cancy compound has been reported in bulk Cu-In-Se studies (Hoenle et al.,
1988). In spite of the apparently orderly variation of behavior with x =
Ga/(In + Ga) concentration indicated in Fig. 6.11, other evidence suggests that
this CuIn3Ses compound plays a significant role in solar cell performance for
z > 0.3, replacing the standard pi-n model of pCu(InGa)Sep/i-CdS/ZnO/
1.6
1.5
1.4
1.3
1.2
1.I
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Ga/( I n+Ga)
(4
0.9
0.8
0.7
0.6
0.2 0.3 0 . 4 0.5 0.6 0.7 0.8 0.9
G a/( I n + G a )
(b)
Fig. 6.11. Variation of properties of Cu(1nGa)Sez solar cells deposited by four-source vacuum
evaporation as a function of the Ga/(In + Ga) ratio. (a) Band gap, (b) open-circuit voltage,
(c) short-circuit current, mA/cm2, and (d) solar cell efficiency. (Data from Shafarman et al.,
1996.)
Copper Indium Diselenide and Other 1-Ill-VI Materials 209
0.2 0.3 0 . 4 0.5 0.6 0.7 0.8 0.9
Ga/( In+Ga)
(c)
0.2 0.3 0 . 4 0 . 5 0 . 6 0 . 7 0.8 0.9
Ga/( I n+ G a )
(4
n-ZnO) with a p n junction model in which this n-type defect chalcopyrite

material forms a p-n junction with its p t y p e counterpart CuInSez (Schmid
et al., 1993). Defect chalcopyrite materials in the Cu(Inl-zGaz)3Se5 system
have been deposited in thin film form over the range of 0 < x < 1 by coevapo-
ration (Contreras et al., 1996a,b). The band gap of these defect chalcopyrites
is about 0.20 eV larger than an equivalent Cu(In,Ga)Sez material with similar
Ga content. All defect materials of this type prepared to date show very high
resistivity, low mobility, and low carrier concentration, but do seem to show a
change in conductivity type from n-type to p t y p e as Ga is increased beyond
x > 0.3.
A related investigation of secondary phases in the surface of coevaporated
Cu-In-S films shows that In-rich films have an In-rich second phase at both
surfaces, which has the cation ratio of CuIn3S5 (Scheer and Lewerenz, 1995).
The results are interpreted as the formation of a phase of CuIn3S5 at the grain
boundaries of In-rich CuInS:! films. By way of contrast, Cu excess in Cu-In-S
films leads to a segregation of CuS at the front surface of the films, and of
MoS2 at the back Mo/CuInSz interface.
Controlled incorporation of Na and S into the absorber layer of Cu(In,Ga)
Sez solar cells has been investigated. Cu(In,Ga)Sez solar cells are reported
to show appreciable improvement in performance when Na is present at the
growth surface of films deposited by coevaporation (Rockett et al. 1996). Al-
though it is reported that Na segregates rapidly out of the Cu(In,Ga)Sez for
these deposition conditions, it leads to a strong (112) preferred orientation of
the Cu(In,Ga)Sez and apparently improves the cell performance. In a related
investigation of the effects of Na and S during the rapid thermal compound
formation process (Karg et al., 1993) involving Cu/Ga sputtering and Se evap-
oration, a Na-related shallow acceptor state at about 75 meV above the valence
band was identified, and S incorporation apparently led to an increased open-
circuit voltage because of a reduction in electrically active deep trap states
(Rau et al., 1996).
Nakada et al. (1997) investigated the effects of Na on Cu(1nGa)Sez solar
cells by a multistep process in which NazSe and Cu were evaporated simulta-
neously. The hole density could be held in the 10l6 to 1017 range for
a wide range of Cu/(In +
Ga) ratios of 0.4 to 0.8 by the addition of NazSe,
whereas without the NazSe, the hole density dropped below 10l6 cm-3 for
+
Cu/(In Ga) less than 0.8. Solar cell efficiencies of 10 to 13.5% were achieved
over a wide range of Cu/(In + Ga) ratios from 0.51 to 0.96. It was also found
that p t y p e Cu(In,Ga)3Ses phase films, which co-exist with the Cu(In,Ga)Sez
phase for Cu/(In + Ga) < 0.71, could be obtained for the first time with a
hole density high enough t o allow use as an absorber layer for Cu/(In + Ga)
ratios in the range below 0.51, producing a 12% efficient solar cell for Cu/(In
+ Ga) = 0.51.
Copper I n d i u m Diselenide and Other I-III-VI Materials 211
The technique of selenization of metal films has been applied to Cu(1nGa)

Se2 films by Dittrich et al. (1988). High efficiency (> 15%) Cu(1nGa)Sez solar
cells have been prepared by the selenization method (Birkmire et al., 1995).
Cu-In-Ga multilayer films were deposited by sputtering with a Cu/(In Ga)+
+
ratio of 90% and Ga/(In Ga) ratios from 0 to 75%. The films were reacted
in H2Se at 450°C for 90 minutes and then annealed at 500°C and 600°C for
90 minutes in Ar (Maraduchalam et al., 1994). Solar cells were fabricated by
chemical bath deposition of CdS and sputter deposition of a ZnO front contact.
The as-reacted film appears to be nearly a bi-layer with CuInSe2 on the surface
and CuGaSe2 near the substrate. Annealing at 500°C does not change this
situation, but annealing at 600°C in Ar produces a single phase structure.
Several sequential deposition methods have been investigated for the fabri-
cation of efficient Cu(In,Ga)(S,Se)2 thin film solar cells (Zweigart et al., 1994;
Walter et al., 1996). One such process involves the low-temperature deposi-
tion of InaSe3 and Cu precursors followed by selenization. A second process
involves the indiffusion of Cu and (S,Se) into (In,Ga)z(S,Se)3 precursors a t
a high substrate temperature. These approaches lead to quite different film
morphologies than does the coevaporation process, but solar cell parameters
and performance are quite similar.
A two-stage Se vapor selenization of magnetron sputtered metallic precur-
sors and Ga incorporation using a single Cu-Ga (22 at.%) alloy target, was
developed for preparation of well-adherent , large, compact, well-faceted poly-
hedral grain C ~ I n l - ~ G a ~ Sthin
e 2 films with optimum composition of Cu:In:
Ga:Se of 22.95:25.03:1.40:50.63 (Dhere et al., 1994).
A Zno,35Cdo,65S/CuGaSez cell corresponding to z = 1 was made with an
efficiency of 5.8% (Dimmler et al., 1987). Noufi et aZ. C1986c) investigated the
optoelectronic properties and x-ray diffraction patterns of CuGaSe2 thin films
deposited by vacuum evaporation of the elements, as a function of composition.
See Table 6.1 for solar cell parameters for ZnCdS/CuGaSez and CdS/CuGaSez
cells.
CuInS2 has a band gap of 1.5 eV that is an ideal match for the solar spec-
trum, and films based on CuInS2 for solar cells can be prepared by a number of
different processes, much like those for CuInSe2. Mitchell et al. (1988) reported
a ZnO/thin-CdS/CuInS2 solar cell with efficiency of 7.3% and q50c = 0.59 V.
Scheer et al. (1993) repprted a glass/Mo/pCuInS2/n-CdS/nf-ZnO/Alcell
prepared by thermal coevaporation of CuInS2 and chemical bath deposition
of the CdS, with an efficiency of 10.2%. The p t y p e CuInS2 was prepared
with a Cu/In ratio between 1.0 and 1.8; excess copper phases (CuS) were
C(4
120 .
11.8 .
lla .
llr)
112 .
110 *
Fig. 6.12. Dependence of the lattice parameters and the energy gap on the composition z of
CuGa(SezTel-,)2 alloys. (Reprinted with permission from G. Masse et al., J . Appl. Fhys.
74, 1376 (1993). Copyright 1993 American Institute of Physics.)
removed chemically. The corresponding cell parameters were &,c = 0.697 V,

J,, = 21.5 mA/cm2, and f f = 0.69. Codeposition of the elements and sequen-
tial deposition processes have been compared for CuInS2 with the conclusion
that both types of processes lead to device efficiencies of 11 to 12% (Walter
e t al., 1995). In,(OH,S), has been used to replace CdS as a buffer layer in
11.4% efficient solar cells based on CuInS2 (Braunger et al., 1996). An in-
vestigation of the majority and minority carriers' phototransport properties
in polycrystalline CuInSa led to a density of states with four bands: shallow
donors and shallow acceptors, and deep donors and deep acceptors that control
recombination processes, centered between 0.3 and 0.5 eV below the conduc-
tion band and above the valence band, respectively (Lubianiker et al., 1996).
Properties of CuInS2 thin films prepared by spray pyrolysis have been investi-
gated (Ortega-Lopez and Morales-Acevedo, 1996), showing promise for use in
solar cells.
CuGa(Se,Te)z bulk materials and thin films have been investigated by
Masse et al. (1993). These alloys can be grown with p t y p e conductivity
and with a good lattice match to CdS for a Se:Te ratio giving a band gap close
to 1.5 eV. Thin films were grown using a CSVT technique, with iodine as the
reagent. The dependence of band gap and lattice constants on Te/Se ratio is
shown in Fig. 6.12. Good-quality CuGaSe2 thin films were easily grown, but
CuGa(Se,Tel-,) thin films could not be obtained when 5 < 0.5, as is expected
Copper I n d i u m Diselenide and O t h e r I-III-VI Materials 213
from the CuGaTe2 phase diagram. Thermal evaporation gave similar results,
but flash evaporation gave thin films with a composition close to that of the
source.
A general multinary system of form C u ~ _ , A g , I n ~ ~ y ~ , G a y A 1 , S e ~ ~ l ~ , ~ ,
S2,TezW has been modeled by Dhingra and Rothwarf (1996), including graded
band gap effects to improve the open-circuit voltage without sacrificing the
short-circuit current in CuInSea/CdS solar cells. The model is based on a pi-
n structure with the graded bandgap material being the intrinsic region. Higher
efficiency appears to be possible as a result of confining the incident light in the
intrinsic region to achieve higher absorption efficiency, grading the conduction
and valence bands to improve electron and hole collection efficiency with op-
timal grading being linear from 1.5 to 1.3 eV, and tailoring the recombination
region to minimize recombination and achieve higher open-circuit voltage.
6.6. M u l t i j u n c t i o n Cells
A number of multijunction or stacked cells have involved a CuInSez solar cell

as one of the components. Some of these have been mentioned in earlier chap-
ters and are summarized here for convenience. (1) A GaAs/CuInSez multi-
junction gave an efficiency of 21.3% for a four-terminal device consisting of
a GaAs CLEFT thin film top cell and a ZnCdS/CuInSez thin film bottom
cell (see Sec. 4.5). (2) Laminated four-terminal multijunction cells combining
a-Si:H and CuInSe2 cells have been developed (see Sec. 3.10). (3) Similar cells
have been prepared using vacuum evaporation from elemental sources for the
CuInSe2, and photochemical vapor deposition for the a-Si:H cell (McCand-
less et al., 1988). (4) Also investigated is a multijunction cell consisting of
CdHgTe/CuInSez (Meakin et al., 1986).
6.7. General M a t e r i a l s C o n s i d e r a t i o n s
The fabrication and use of CuInSe2 solar cells raises several questions in the
areas of health and safety, and the supply of key elements (Zweibel and Barnett,
1993).
Hazardous chemicals like H2Se and Cd are involved in the fabrication and
structure of these cells. H2Se is a highly toxic gas but it can be used safely
provided that certain well-known safety precautions are used (Moskowitz et al.,
1986;Bottenberg and Sproull, 1988). Risks associated with it can be minimized
if the gas is produced on-site and is recycled after use. Sources of Se are being
sought that would eliminate the need for H2Se completely.
The toxic dangers associated with Cd are certainly less in the CdS/CuInSez
cells than in the CdS/CdTe cells, for which the issue has been discussed in
Chapter 5, because of the smaller amount of Cd involved.
The use of Se in the cells requires proper disposal techniques to avoid
contamination of groundwater. These appear to be available.
If CuInSe2 cells enter into large-scale production, the availability of In might
become an issue. Although it appears that there is a sufficient abundance of
In to meet the growing demand of an effective solar cell market, there could
be a conflict between supply and demand. Requirements for large amounts of
In could be reduced by using thinner layers of CuInSe;! made possible by the
high absorption constant, using CuGaInSe2 alloys in which about 25% of the
In is replaced by Gal and recycling cells after 30 years.
CHAPTER 7
OTHER MATERIALS OF INTEREST

FOR SOLAR CELLS
7.1. Overview
Earlier in this book we have stressed the fact that the actual number of dif-
ferent materials capable of being used as the light-absorbing material in sta-
ble, highly efficient, semiconductor junction, solar cells is strikingly small: Si,
GaAs, CdTe, and CuInSe2, with variations due to material structure and re-
lated alloys, represents the whole list. In this final chapter we take a brief look
at some of the other materials and structures that either have been promising
at some time in the past, or might be promising in the future, which have not
been discussed previously in this book. Since 1993 a summary of the highest
confirmed efficiency for a range of photovoltaic cells has been published every
six months, including new entries as they qualify (Green, 1996).
7.2. Cuprous Oxide

In spite of the fact that CuaO has a direct band gap of 1.95 eV, somewhat large
to match the solar spectrum, it has been thought attractive at various times in
spite of its low efficiency, because of its very low production costs (Chopra and
Das, 1983). Heating a Cu substrate in air at 1050°C allows the formation of
fairly well oriented Cu20 films, with a Schottky barrier being formed between
the Cu substrate and the Cu2O film. Deposition of an ohmic contact (e.g. Cu
or Ni) to the Cu2O completes the back-wall cell. Alternatively a metal layer
can be deposited on the Cu20 film to form a front-wall Schottky device.
Back-wall cells prepared by Olsen and Bohara (1975) are in effect MIS
devices. Although it was suggested that efficiencies of 10% could be achieved
by careful cell design, actual solar cell parameters were typically & = 0.37 V,
J,, = 7.7 mA/cm2, f f = 0.57 and efficiency = 1.6%. Just as the simple
fabrication process of the Cu,S/CdS cell could not make that cell practically
useful because of its inherent instabilities, as described in Sec. 1.2, so the almost
ideally low cost and simplicity of the fabrication process of the Cu/CuzO cell
could not make that cell practically useful because of its low efficiency.
215
7.3. Zinc Phosphide

A careful search of the catalogue of possible materials suitable for solar cells
led to the choice of ZnsPz as a potentially ideal new material (Catalano
et al., 1978). It has a band gap of 1.5 eV and a high absorption constant
(> lo5 cm-l), and can be readily prepared in thin-film form with p t y p e con-
ductivity from inexpensive and available elements. In addition, Fe makes an
excellent substrate for Zn3Pz films, since it has good lattice match and similar
coefficient of thermal expansion, and forms a low-resistance ohmic contact. A
closed-tube horizontal vapor transport system was used for the growth of large
single crystals of Zn3Pz with and without iodine chemical transport; the as-
grown resistivity of these crystals was about 50 ohm-cm (Wang et al., 1981a,b).
Schottky barrier Mg/ZnsPz junctions on single crystal Zn3Pz showed solar cell
efficiency of 6% (Bhushan and Catalano, 1981). Thin films can be grown by
CSVT in Ar with large grains and long minority carrier diffusion lengths (0.5-
4 pm). Schottky barrier cells using these polycrystalline films gave a total area
efficiency of 4.3% (Bhushan, 1982).
Luminescence pair transitions (Briones et al., 1981), ac-photoconductivity
spectral response (Wang and Bube, 1982), electrical conductivity and Hall
effect of sublimed and iodine-transport grown crystals (Wang et al., 1982),
and DLTS spectra corresponding to deep majority-carrier traps (Suda and
Bube, 1984) have been investigated for Zn3Pz single crystals. It was found
that vacuum evaporated contacts of Ag, Au or a Au/Ag alloy all exhibited
linear current-voltage curves over the temperature range of interest. Three
main deep hole traps were observed by DLTS with activation energy of 0.20,
0.36 and 0.73 eV from the top of the valence band; the densities of these levels,
however, depended strongly on the thermal history of the sample.
Zn3Pz has not fulfilled its promise because of difficulties in obtaining good
junction properties. In general n-type material could not be fabricated and
thus n-p junctions were not possible. Only high-resistivity n-type ZnsPz
( n < 10'l cmP3), not suitable for solar cell applications, has been produced
by MBE techniques (Suda et al., 1996). Schottky barriers on p t y p e material
do not follow a simple variation of barrier height with metal work function,
and continuing research revealed that Mg/Zn3Pz junctions were the only junc-
tions that showed the required electrical properties for solar cell fabrication.
Attempts were made to prepare n-p junctions between Zn3Pz crystals and
n-type vacuum evaporated CdS, DC-sputtered CdO, CVD ZnO, and electron-
gun vacuum evaporated I T 0 (Wang et al., 1982). All results were similar:
high leakage currents in the dark and small photovoltaic effects. Similarly
Copper Indium Daselenide and Other I-111- V1 Materials 217
attempts to fabricate solar cells using n-ZnSelpZnsP2 or n-ZnCdS/pZnsPa

heterojunctions were unsuccessful (Bhushan, 1984).
The reasons behind these materials problems with Zn3P2 were clarified by
an investigation of the phenomena occurring at the surface of bulk polycrys-
talline Zn3P2 and at interfaces of Zn3P2-based devices (Casey et al., 1987).
(1) Electrical measurements of Mg/ZnsPa junctions formed on annealed ZnsP2

surfaces, and analyses of similar surfaces by Auger electron spectroscopy,
indicated that loss of P from a very thin surface region is sufficient to
severely degrade diode characteristics. Auger spectroscopy evidence for
the surface loss of P when heated by an electron beam is shown in Fig. 7.1.
0 2 4 6
Time (minutes)
8
i10
Fig. 7.1. Data from Auger spectroscopy on a Zn3Pz surface left under the electron beam,
showing a decrease in the magnitude of the P signal with time. (Reprinted with permission
from S. Casey et al., J . A p p l . Phys. 61, 2944 (1987). Copyright 1987 American Institute of
Physics).
(2) Surface photovoltage measurements showed that at the surface of as-etched

or as-polished ZnsP2, the energy bands are nearly flat. The sign of the
surface photovoltage is negative, indicating a depleted surface for p t y p e
ZnsP2, but unlike the cases for CdTe and InP examined for comparison,
there is no energy barrier to majority carriers for either etched or polished
Zn3P2 surfaces. The observed barrier on p t y p e CdTe or InP correlated
with the difficulty in producing ohmic contacts to these materials, while the
absence of a surface barrier on pZn3P2 is consistent with the observation

that ohmic contacts are almost inevitable, but barriers are difficult to form.
(3) High-frequency capacitance measurements of Al/A1203/Zn3P2 structures
indicated that a high interface state density (> 1013 eV-' cm-') prevents
barrier formation by pinning the surface Fermi level. As shown in Fig. 7.2,
these interface state densities are one order of magnitude larger than those
measured on A1203 electron-beam evaporated on I n P (Favennec et al.,
1979), two orders of magnitudes larger than those measured on A1203
electron-beam evaporated on Si (le Contellec and Morin, 1978), and almost
four orders of magnitude larger than the results of similar analysis on an
Al/SiO2/SiMOS device (Akinwande, 1987).
I
101~
'-Pi
-/-
I
/'AL20,/Si
al
:
v)
10'0
Fig. 7.2. Calculated surface state density as a function of semiconductor surface potential for
an AI/A1203/Zn3P2 device. Also shown are the results of similar experiments with A1203
electron-beam evaporated on Si (le Contellec and Morin, 1978) and InP (Favennec et al.,
1979), and the results of a similar analysis on an AI/SiOz/SiMOS device (T. Akinwande,
1987). (Reprinted with permission from S. Casey et al., J . A p p l . Phys. 61,2944 (1987).
Copyright 1987 American Institute of Physics).
7.4. Tungsten Diselenide

A compound with apparently promising properties is WSe2, with a direct band
gap of 1.35 eV, an extremely high optical absorption coefficient (> lo5 cm-l
Copper Indzum Diselenide and Other I-III-VI Materials 219
over most of the range above its band gap energy, like CuInSez), excellent
chemical stability, and the possibility of being prepared in either n- or p t y p e
form. Schottky barrier AllpWSez solar cells have been prepared with an
efficiency of 5.3% (Clemen and Bucher, 1978). Difficulties were encountered
with depositing films with the required structural properties for this layered
material (Miller, 1981).
7.5. Polymers and Organic Materials

A fairly steady effort has been made to discover or fabricate an organic material
suitable for use in solar cells. A review of organic photoconductors and pho-
tovoltaics is given by DiMarco and Giro (1994). In general organic materials
have large energy gaps and low electrical conductivities, light absorption pro-
duces excitons not mobile carrier pairs, and the generation of mobile charges
is strongly field dependent. The generation of photocurrent is by light ab-
sorption, exciton creation, exciton diffusion, exciton dissociation in the bulk or
at the surface, field-assisted carrier separation, carrier transport, and carrier
delivery to the external circuit. Models used to describe photovoltaic effects in-
volve either Schottky-barrier type models, models based on the photoinjection
of charges at the electrode interfaces, or p n junction models formed between
a p t y p e and an n-type organic material.
The attempt to use organic materials as the absorber layers in solar cells
usually results in only low solar efficiencies because of the short minority car-
rier lifetimes and large series resistance characteristic of such materials. Al-
though the monochromatic quantum efficiency of organic materials can ap-
proach loo%, the total quantum efficiency for the solar spectrum is quite low.
Examples are Cr/(chlorophyll-a)Hg junctions that give qboc = 0.2-0.5 V and
a monochromatic conversion efficiency of 0.016% for illumination at 0.745 pm
(Tang and Albrecht, 1975a,b), and a cell based on a merocyanine dye absorber
layer giving &c = 1.2 V, J,, = 1.8 mA cm-’ and solar efficiency of 0.7%
(Morel et al., 1978).
The molecular structures of several materials that have been tested in a
Schottky-type cell, with an organic compound sandwiched between two met-
als, are given in Fig. 7.3. In the Schottky structure, illumination is through
one of the two semitransparent metal electrodes. Films of these materials have
been deposited by vacuum sublimation, spin coating, and electrochemical de-
position. Most organic materials show p t y p e conductivity, so that the ohmic
contact is a high-work-function metal such as Au or Ag, or IT0 conducting
glass, while the rectifying contact is a low-work function metal such as A1 or
8
@$...+"...N$
N13N
Fig. 7 . 3 . Molecular structures of some interesting organic materials: (a) copper phthalo-
cyanine (CuPc); (b) perylene tetracarboxylic derivative (PV); (c) hydroxysquarylium; (d)
merocyanine dye. (Reprinted with permission from P. Di Marco and G. Giro in Organic Con-
ductors, p. 791 (1994) by courtesy of Marcel Dekker Inc., Copyright 1994, Marcel Dekker,
NY).
In. Reasonable open-circuit voltages are produced, but only small short-circuit
currents. Solar efficiencies are usually less than 1%.
In p-n junction cells, illumination can be through a transparent electrode
onto the n-type material, chosen to be the shorter-wavelength absorber with
a fluorescence band that overlaps the absorption band of the p t y p e material.
A notable improvement over earlier work was obtained by Tang (1986) using
a cell pictured in Fig. 7.4, composed of ITO/copper-phthalocyanine (CuPc,
ptype)/perylene tetracarboxylic derivative (PV, n-type)/Ag. Under AM2
C o p p e r I n d i u m Diselenide a n d O t h e r I-III-VI Materials 221
Gold Wire Contact
I
I
t
Light
Fig. 7.4. Schematic diagram of a p n organic cell between p t y p e CuPc, and n-type PV.
(Reprinted with permission from C. W. Tang, A p p l . Phys. Lett. 48, 183 (1986). Copyright
1986 American Institute of Physics).
illumination, a solar efficiency of 1% was achieved without correction for re-

flection or absorption losses.
The performance of polymer photovoltaic cells is greatly enhanced by the
introduction of a network of internal donor-acceptor heterojunctions (Yu et al.,
1995). The semiconducting polymer is blended with c60 or its more solu-
ble derivatives. Composite films of poly(2-methoxy-5-(2'-ethyl-hexyloxy)-l,4-
phenylene vinylene) (MEH-PPV) and fullerenes have a collection efficiency of
about 0.29 electrons per photon, and an energy efficiency of about 2.9%, val-
ues that are about two orders of magnitude larger than those obtained with
devices made with pure MEH-PPV. The process depends upon the transfer of
photoinduced electrons from the MEH-PPV (as donor) to c 6 0 (as acceptor),
via a bicontinuous network of internal donor-acceptor heterojunctions. Further
research is focused on decreasing internal resistive losses, and optimization of
the blend composition and network morphology.
Non- Organic Polymers

Sulfur nitride (SN), is a material that has the possibility of behaving as a
highly anisotropic semimetal with a high DC conductivity (> lo3 ohm-'cm-')
along the polymer chains at room temperature (Chiang et al., 1976). Mak-
ing it of interest for Schottky barrier cells is the observation that (SN), has
a larger work function than any of the elemental metals (Scranton et al.,
1976;Best et al., 1976). A polymer/semiconductor solar cell has been investi-
gated using a (SN),/n-GaAs structure (Cohen and Harris, 1978). Open-circuit
voltages greater than 0.70 V were obtained, compared to a value of 0.49 V

for a Au/GaAs structure on the same GaAs, and without optimization a solar
efficiency of 6% was obtained.
A similar metallic polymer is polyacetylene (CH),, which has a band gap
of about 1.6 eV and can be doped either n-or p t y p e . Homojunctions, hetero-
junctions with ZnS and CdS, and Schottky barriers with Ba, all show a large
built-in voltage, but they appear to have low quantum efficiencies for solar il-
lumination because of small minority carrier diffusion lengths (Waldrop et al.,
1981).
7.6. Semiconductor/Liquid Junctions

An introduction to photoelectrochemical (PEC) cells was given in Sec. 1.3 with
descriptions in Fig. 1.12. Such cells use a junction between a semiconductor
and an electrolyte to convert light to electrical and/or chemical energy. Most
PEC cells are quite similar to Schottky barrier solar cells, with a depletion
layer forming in the semiconductor and the metal layer replaced by a highly
conductive electrolyte and a counter electrode. In the photovoltaic application,
of principal interest to us here, charge transport through the electrolyte is
accompanied by various redox reactions that leave the electrolyte and hopefully
also the semiconductor electrode unchanged.
A review of recent developments has been given by Lewis (1995). Standard
semiconductors useful in solar cells are not generally useful in photoelectro-
chemical cells with an aqueous electrolyte. Silicon photoelectrodes, for exam-
ple, form an insulating layer of silicon dioxide on exposure to light. GaAs
photoelectrodes dissolve away when illuminated. Fujishima (1972) found that
titanium dioxide was a stable electrode in the light-driven electrolysis of water
into hydrogen and oxygen gases, but the band gap of T i 0 2 is too large for
effective conversion of solar energy and produced a solar efficiency of only 1%.
Subsequent research indicated that all other materials with smaller band gaps
than Ti02 (e.g. materials obtained by replacing the oxygen in Ti02 by sulfur,
selenium or tellurium) were unstable and would eventually corrode.
It has been reported that the corrosion of silicon and other semiconductor
photoelectrodes can be prevented by use of a noble metal coating (Tsubomura
and Nakato, 1984). A photoelectrochemical cell was developed composed of a
noble-metal-coated p-n junction Si photoanode, a counter Pt electrode, and a
cation exchange membrane, by which HI is efficiently decomposed into hydro-
gen and iodine. A solar to chemical conversion efficiency of 8.2% was reported.
The use of nonaqueous photoelectrochemical cells, containing organically-

based electrolytes, overcomes some of the difficulties and allows the use of
semiconductors such as silicon that are unstable in water. In a nonaqueous
photoelectrochemical cell, the carriers generated in the semiconductor by il-
lumination are transferred to a stabilizing chemical reagent in the electrolyte
solution that accepts an electron a t one electrode and donates an electron at the
other electrode. The stabilizer itself does not undergo a net chemical change.
An example of such a cell (Lewis, 1995) is one in which the semiconductor
is silicon, the nonaqueous electrolyte consists of an organic solvent (propylene
carbonate), a salt (lithium perchlorate) to provide electrical conductivity, and
soluble ions (an organometallic iron complex) to carry the electrical charges
through the liquid. Solar efficiencies of 12 t o 14% are reported for such cells.
The efficiency of the cell can be optimized by selecting the chemical design of
the electrolyte, the photoelectrode material, and the stabilizing agent. Stable
photoelectrochemical calls in nonaqueous solutions have been made with Si,
GaAs, InP, and some other semiconductors with suitable band gap.
Another approach to photoelectrochemical cells involved immersing small
silicon solar cells in an electrolyte, so that the current generated by the cells
is used directly to electrolyze a halogen acid, such as HBr (Johnson, 1981;
Bawa and Chang, 1985). The hydrogen and bromine produced can be stored
separately and then recombined in a fuel cell to produce electrical energy on
demand.
Some success has also been achieved in obtaining increased quantum yields
on large-band-gap materials such as Ti02 by the use of surface dyes (O’Regan
and Graetzel, 1991). Such dyes have extended the absorption range of Ti02
into the visible portion of the spectrum. Systems with nonaqueous solvents
permit greater stability and a wider choice of dye materials; solar efficiencies
greater than 6% have been reported.
7.7. New Materials and Structures

A review of new materials and structures for photovoltaics has been given
by Zunger et al. (1993). These include nontraditional alloys, materials with
reduced dimensionality, spontaneously ordered alloys, interstitial semiconduc-
tors, filled tetrahedral structures, ordered vacancy compounds, and compounds
based on d and f electron elements. A major motivation in the design of these
new materials is the ability to achieve band gap tuning and lattice matching
simultaneously.
Superlattices and multilayer structures offer the potential for producing

devices with tunable properties. An a-Si:H solar cell has been developed with
a player with a superlattice structure (Tsuda et al., 1985; Arya et al., 1985);
an increase in the band gap and doping of the player in an otherwise normal
pi-n a-Si:H structure resulted in a n increase in open-circuit voltage.
Wronski et al. (1987a,b,c) describe research on a-Ge:H/a-Si:H superlattices
used in a Pt Schottky barrier solar cell structure. They show the existence of
quantum size effects in amorphous semiconductors, a shift in the optical and
carrier transport edges as a function of the thicknesses of the layers, and the
possibility of efficient collection of carriers photogenerated in the barrier region.
Research on a-Si:H,F/a-SiGe:H,F multilayer superlattices by Conde et al.
(1987, 1988a,b) indicate that optical band gap, photo-and dark conductivities,
and carrier collection can be tuned within limits.
An increase in efficiency of p-i-n structures has been sought by the incor-
poration of quantum wells (Barnham et al., 1991). The application of these
ideas to InP solar cells with lattice matched Ino.53Gao.47As multiple quantum
wells makes use of the fact that strain free InGaAs wells can be incorporated
in the i-region, which are deeper than for any other material used in this way
(Freundlich et al., 1994; Anderson and Wojtczuk, 1996; Zachariou et al., 1996).
Conversion efficiencies of 9 5 2% have been achieved.
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INDEX
cadmium sulfide, CdS nanoparticle precursors, 174

chemical bath deposition (CBD), role of oxygen, 170, 171
179-181 spray pyrolysis, 171-174
CdS/CdTe solar cells, 155 vacuum evaporation, 164
CdS/CuInSez solar cells, film deposition procedures for
185-188 other 11-VI materials,
CdS/InP solar cells, 126, 127 175-1 81
Cu,S/Cds solar cells, 15 chemical bath deposited
replacement of, in (CBD) for CdS, ZnS,
CdS/Cu(In,Ga)(Se,S): 179-18 1
solar cells, 204 chemical vapor deposition
(CVD), 175
cadmium telluride, (CdTe), 135-182 electrodeposition, 176
alloys, 181, 182 screen printing, 175
Hg,Znl-,Te, 182 sputtering, 177
atomic force microscopy (AFM), grain-boundary effects, 160-164
158 grain-boundary state densities,
CdS/CdTe solar cell design rules, 163
155 health and safety, 137
CdSI-,Te, formation at interface, interface properties, 154-159
156-158 MIS junctions, 145
contact properties, 141-144, oxidation of surface, 144-146
146-149 post-deposition processing,
CuAu alloy, 147 154-159
diffused Li, 148 SIS junctions, 159, 160
doping of p t y p e material, solar cell summary, 137-140
149-154
surface properties, 141-144
CdsAsz source, 150
CVD and MOCVD doping, 149
ion-assisted doping, 151-154 copper indium diselenide, CuInSe2
ion implantation doping, 149 (CIS), 184-214
photon-assisted doping, 150 alloys and related materials,
type-conversion/junction- 206-213
formation (TCJF), 156 CuGa,Inl -,Sez/ZnCdS
film deposition procedures for heterojunctions, 207
CdTe, 164 CuGa(Se,Te)z, 212
close-spaced vapor transport CuInsSes, 207
(CSVT), 167 CuInSz, 211
close-spaced sublimation (CSS), dependence of properties on
167-171 Ga/(In+Ga) ratio, 207-210
hot-wall vacuum evaporation, CdS/CuInSeZ solar cells,
165 185-188
277
278 Index
CuInl-,GazSe2 solar cells, 188 gallium arsenide, GaAs solar cells,

fabrication techniques, 196-201 111-126
close-spaced vapor transport efficiency vs. date and type of
(CSVT), 200 cell, 114, 117
electrodeposition, 200 fabrication techniques, 115, 116
MOCVD, 198 liquid phase epitaxy (LPE),
molecular beam epitaxy (MBE), 115
201 metalorganic chemical vapor
selenization of metal layers, 197 deposition (MOCVD), 115
single-crystal growth, 196 general properties, 112-115
spray pyrolysis, 199 solar cell development, 116-126
sputtering, 199 AlGaAs/GaAs heteroface
vacuum evaporation, 196, single junction cells, 116
materials properties, 19G-196 efficiency vs. light concentra-
contacts, 196 tion, 117, 118
crystal defects, 191 epitaxial lift-off (ELO) tech-
crystal structure, 191 nique, 119.
health and safety, 213, 214 Ge substrate, 118
interface properties, 194 CLEFT films, 121
minority carrier diffusion hybrid multijunction cells, 131
length, 192 GaAs/CuInSez, 131
optical absorption, 193 GaAs/GaSb, 132
oxidation of CuInSe2, 194 GaAs/Si, 131
thermal stability, 195 GaInPz/GaAs, 131
solar cell developments, InP/GaInAs, 132
201-206 In,Gal-,As alloys, 122
additional insights, 204, 205 MIS cells, 121
air bake effects, 202, 203 multicrystalline or tandem
effect of Na, 210 cells, 122-126
efficiency, 189 GaInAsP alloys, 124
flexible substrates, 206
multijunction cells, 213
replacement of CdS film in I-111-VI materials, 184
CdS/Cu(In,Ga)(Se,S)2solar
cells, 204 11-VI heterojunctions, 136, 183
selenization of metal layers,
203, 204 indium phosphide, InP solar cells,
sequential deposition methods, 126-13 1
211 epitaxial film cells, 128
three-source-vacuum evapora- heteroface cells
tion, 201-203 CdS/InP, 127
cuprous oxide, CuzO, 215 ITO/InP, 128
heterojunction cells, CdS/InP,
electron-beam-induced current (EBIC), 126, 127
165 homojunction cells, 129
Index 279
MIS cells, 129 radiation resistance of 111-V solar cells,

polycrystalline InP cells, 129 132-134
photovoltaic materials, examples of, 32 reference information on

photovoltaics, 11
photovoltaic models, 25-32
collection function, 25-28 silicon, Si, hydrogenated amorphous
(a-Si:H), 68-110
advantages and disadvantages, 68,
photovoltaic processes, 2 ff. 69
applications, 12
alloys, 106-108
areas of concern, 13 a-Si:Ge:H, 106-108
efficiency, 8 a-Si:C:H, 106-108
fill factor, 8 band-tail states, 72
important materials properties, 10 dangling bond defects, 71-74
junctions, types of, 16-24 defect generation, 74-79
buried homojunctions, 21 dopants, 74
heteroface, 21 electron beams, 78
heterojunction, 18-21 forward currents in devices,
homojunctions, 17 78
photoelectrochemical, 24, 222, kinetics of defect formation,
223 76
pi-n, 23 optical generation, 75-78
Schottky barrier, 22 space-charge region, 78
SIS, 21 stretched-exponential descrip-
transport processes, 28-32 tion, 76
diffusion, 28 thermal generation, 74
interface recombination models for dangling bond defects,
without tunneling, 30 79-9 1
recombination in depletion configurational coordinate dia-
layer, 30 grams, 79
thermally assisted tunneling, defect pool model, 80
31 discrete energy level models,
tunneling without thermal 84-91
assistance, 31 single trivalent defect,
open-circuit voltage, 3 85-87
short-circuit current, 2 two trivalent defects,
simplest device, 5 87-91
ideality factor, 6 carrier-induced model, 83
reverse saturation current, 6 impurity-induced defects, 82
superlattices, 224 rehybridized two-site model, 82
weak-bond breaking, 80
polymers, 219-222 deposition techniques, 96, 97
non-organic polymers (SN), , dispersive phenomena, 76
(CH),, 221, 222 mobility edge, 73
280 Index
mobility gap, 73 silicon substrates, 62

random network, continuous, 73 silicon sheets from powder, 62
solar cells, types of, 70, 91-96
hybrid solar cells, 109 silicon, Si, single crsytal
stability of solar cells, 100-106 Auger recombination, 37, 56
evidence related to density of doping, 36
defects, 100-105 electron/hole capture cross sec-
optical degradation, 102 tion, 39
other suggested causes for in- gettering, 38
stability, 105, 106 growth, 35
transport properties, 97-100 lifetime, 36
mobility-lifetime product, 99 light-trapping, 45
passivation, 40, 45
silicon, Si, crystalline, 34-67 processing summary from FZ, CZ
non-single-cryst a1 silicon, types of, and mc-silicon, 49-53
34 rapid thermal processing, 52
recombination, sources of
bulk, 37
silicon, Si, microcrystalline (pc-Si), 66,
contact area, 41
67
dislocations, 53
heterojunction cells, 67
effects of solar concentration,
p-2-71 cells, 67
46
Shockley-Read recombination,
silicon, Si, microcrystalline (mc-Si) 37
solar cells, 57-66 surface, 39
advantages and problems, 57 solar cells, 36, 41-56
cast multicrystalline wafers, 60 Back Point-Contact cell,
continuous casting, 61 45-48
conventional casting, 60 Comsat non-reflective (CNR)
electrc-magnetic casting, 61 cell, 44
heat exchanger method, 61 efficiency, ways to increase,
contactless characterization 53-56
methods, 65 current increase, 53, 54
light-beam induced lumines- voltage increase, 54-56
cence, 66 novel structures, 56, 57
modulated free-carrier absorp- spheres of silicon in perfo-
tion, 65 rated A1 foil, 56
foreign substrates, 62 superlat t ices, 57
grain boundary effects, 58-61 tandem junction cells, 56
passivation procedures, 64 vertical multijunction cells,
multilayer thin film cells, 65 56
“ribbon” technology, 61 Passivated Emitter, Rear
dendritic web, 61 Locally-Diffused cell, 48
edge-defined film-fed growth, typical solar cell, 41-44
61 violet cell, 44
Index 281
solar spectrum, 5
air mass. 5
tungsten diselenide, WSe2, 218
zinc oxide, ZnO, 179
zinc phosphide, ZnaPz, 216-218
zinc telluride, ZnTe, 147
Zn,Cdl-,Te films, 182

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Photovoltaic Materials

SERIES ON PROPERTIES OF SEMICONDUCTOR MATERIALS

Series Editor: Ron C. Newman

Semiconductor Defect Modelling ab initio Methods

Muon Spectroscopy of Semiconductors

Complex Semiconductor Defects

Imperial College Press

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Copyright 0 1998 by Imperial College Press

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Printed in Singapore by Uto-Print

This book is dedicated to Betty Jane Meeker Bube,

Stanford 1997 Richard H. Bube

5.2. Surface and Contact Properties 141

The Photovoltaic Process

Maximizing Photovoltaic Performance

Description of Solar Spectrum

Simplest Photovoltaic Device

and the short-circuit current is controlled only by the photoinduced current

illumination is zero (open-circuit condition), then solution of Eq. (1.1) for J = 0

Jsc = Jo[exp(PPoc/AkT) - 11 (1.4)

7 = P m / P r a d = Jmd’m/Prad = Jsc4oc.f f /Prad (1.5)

ff = Jm4mf Jsc4oc (1.6)

Eg ' ,¶" 19.2%

Summary of Important Materials Properties

All five of these areas of materials properties must be carefully designed

1.2. Applications of Photovoltaics

What Photovoltaic Energy is Available?

Main Areas of Concern f o r Photovoltaics

(1) The achievable efficiency with a particular photovoltaic system is highly

The Illustrative Case of Cu,S/CdS Solar Cells

or by oxidation of Cu a t the free surface of Cu,S, and results in a degradation

1.3. Types of Semiconductor Junctions

characteristic energy-band structure for each of these junctions in this section.

Table 1.1. Material considerations for use in a heterojunction solar cell.

Band gap of smaller band-gap material Direct gap near 1.4 eV

Diffusion length Long electron diffusion length in p t y p e material

Sometimes a variation on the p n heterojunction between two semiconduc-

Buried Homojunctions or Heteroface Junctions

A typical energy band diagram for a Schottky barrier on an n-type ma-

semiconductor, a Schottky barrier is formed if qc$M < q@s,and holes flow

1.4. More D e t a i l e d P h o t o v o l t a i c Models

Differences between Dark and Light Conditions

J d = yd{J,”exp [ad(4- J d R t ) ]+ 4/R,d - J,”}

where the superscript d denotes the dark condition, yd = 1/(1 + Rt/R,d),

g(4) = 1 - exp[-aw(4)1/(1 +G J (1.12)

h(4) = 1/(1+ s r / m (1.14)

Fig. 1.12. Spectral dependence of the quantum efficiency for a n n - C d S l p C d T e heterojunc-

An example of the qualitative effects of these collection functions is given

increasing E a t the interface, and/or decreasing SI through its own voltage

Other Photovoltaic Parameters

4oc= (l/a')ln[H(4oc) (JL/JA) +1 - 4oc/JARk] (1.15)

Junction Transport Processes

Foward bias current transport

with a d i f f = q/kT and A = 1, and

where, in the p t y p e material, ni is the intrinsic carrier density, N A is the

Recombination an depletion region

Interface recombination without tunneling

where SI is the electron capture cross-section of interface states with density

Tunneling limited recombination through interface states without

Jti = J,[exp(a/kT - 11 (1.24)

with a = (47r/h) ( & m * / N ~ )independent